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Sample records for boracite-network-topology porous mof

  1. Activation of porous MOF materials

    Science.gov (United States)

    Hupp, Joseph T; Farha, Omar K

    2013-04-23

    A method for the treatment of solvent-containing MOF material to increase its internal surface area involves introducing a liquid into the MOF in which liquid the solvent is miscible, subjecting the MOF to supercritical conditions for a time to form supercritical fluid, and releasing the supercritical conditions to remove the supercritical fluid from the MOF. Prior to introducing the liquid into the MOF, occluded reaction solvent, such as DEF or DMF, in the MOF can be exchanged for the miscible solvent.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-05-08

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

  3. A “green” strategy to construct non-covalent, stable and bioactive coatings on porous MOF nanoparticles

    Science.gov (United States)

    Agostoni, V.; Horcajada, P.; Noiray, M.; Malanga, M.; Aykaç, A.; Jicsinszky, L.; Vargas-Berenguel, A.; Semiramoth, N.; Daoud-Mahammed, S.; Nicolas, V.; Martineau, C.; Taulelle, F.; Vigneron, J.; Etcheberry, A.; Serre, C.; Gref, R.

    2015-01-01

    Nanoparticles made of metal-organic frameworks (nanoMOFs) attract a growing interest in gas storage, separation, catalysis, sensing and more recently, biomedicine. Achieving stable, versatile coatings on highly porous nanoMOFs without altering their ability to adsorb molecules of interest represents today a major challenge. Here we bring the proof of concept that the outer surface of porous nanoMOFs can be specifically functionalized in a rapid, biofriendly and non-covalent manner, leading to stable and versatile coatings. Cyclodextrin molecules bearing strong iron complexing groups (phosphates) were firmly anchored to the nanoMOFs' surface, within only a few minutes, simply by incubation with aqueous nanoMOF suspensions. The coating procedure did not affect the nanoMOF porosity, crystallinity, adsorption and release abilities. The stable cyclodextrin-based coating was further functionalized with: i) targeting moieties to increase the nanoMOF interaction with specific receptors and ii) poly(ethylene glycol) chains to escape the immune system. These results pave the way towards the design of surface-engineered nanoMOFs of interest for applications in the field of targeted drug delivery, catalysis, separation and sensing.

  4. Highly Porous Carbon Derived from MOF-5 as a Support of ORR Electrocatalysts for Fuel Cells.

    Science.gov (United States)

    Khan, Inayat Ali; Qian, Yuhong; Badshah, Amin; Nadeem, Muhammad Arif; Zhao, Dan

    2016-07-13

    The development of highly competent electrocatalysts for the sluggish oxygen reduction reaction (ORR) at cathodes of proton-exchange membrane fuel cells (PEMFCs) is extremely important for their long-term operation and wide applications. Herein, we present highly efficient ORR electrocatalysts based on Pt/Ni bimetallic nanoparticles dispersed on highly porous carbon obtained via pyrolysis of a metal-organic framework MOF-5. In comparison to the commercial Pt/C (20%), the electrocatalyst Pt-Ni/PC 950 (15:15%) in this study exhibits a pronounced positive shift of 90 mV in Eonset. In addition, it also demonstrates excellent long-term stability and durability during the 500-cycle continue-oxygen-supply (COS) accelerating durability tests (ADTs). The significantly improved activity and stability of Pt-Ni/PC 950 (15:15%) can be attributed to the Pt electron interaction with Ni and carbon support as has been proved in X-ray and microscopic analysis.

  5. A 3D porous zinc MOF constructed from a flexible tripodal ligand: Synthesis, structure, and photoluminescence property

    International Nuclear Information System (INIS)

    A new metal-organic framework, [Zn5(trencba)2(OH)2Cl2.4H2O] (1) [H3trencba=N,N,N',N',N'',N''-tris[(4-carboxylate-2-yl)methyl]-tris (2-aminoethyl)amine], constructed from a flexible tripodal ligand based on C3 symmetric tris(2-aminoethyl)amine, has been synthesized hydrothermally and characterized by elemental analysis, IR, TG, XRD and single-crystal X-ray diffraction analysis. Compound 1 contains an unprecedented linear penta-nuclear zinc cluster fragment. Each ligand links four penta-nuclear fragments, and every fragment links eight ligands to generate a three-dimensional non-interpenetrated porous framework. The uncoordinated water molecules were observed trapped in the void pores. Compound 1 represents the first example of (6,8)-connected 3D bi-nodal framework based on a single kind of organic ligand. The photoluminescence measurements showed that complex 1 exhibits relatively stronger blue emissions at room temperature than that of the ligand. - Graphical abstract: The MOF [Zn5(trencba)2(OH)2Cl2.4H2O] (H3trencba=N,N,N',N',N',N'-tris[(4-carboxylate-2-yl)methyl]-tris (2-aminoethyl)amine) reveals a (6,8)-connected bi-nodal three-dimensional porous framework with unprecedented penta-nuclear fragment, which appears to be a good candidate of hybrid inorganic-organic photoactive materials

  6. Porous carbon as electrode material in direct ethanol fuel cells (DEFCs) synthesized by the direct carbonization of MOF-5

    KAUST Repository

    Khan, Inayatali

    2014-01-12

    Porous carbon (PC-900) was prepared by direct carbonization of porous metal-organic framework (MOF)-5 (Zn4O(bdc)3, bdc=1,4-benzenedicarboxylate) at 900 °C. The carbon material was deposited with PtM (M=Fe, Ni, Co, and Cu (20 %) metal loading) nanoparticles using the polyol reduction method, and catalysts PtM/PC-900 were designed for direct ethanol fuel cells (DEFCs). However, herein, we are reporting PtFe/PC-900 catalyst combination which has exhibited superior performance among other options. This catalyst was characterized by powder XRD, high-resolution transmission electron microscopy (HRTEM), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), and selected area electron diffraction (SAED) technique. The electrocatalytic capability of the catalyst for ethanol electrooxidation was investigated using cyclic voltammetry and direct ethanol single cell testing. The results were compared with those of PtFe and Pt supported on Vulcan XC72 carbon catalysts (PFe/CX-72 and Pt/XC-72) prepared via the same method. It has been observed that the catalyst PtFe/PC-900 developed in this work showed an outstanding normalized activity per gram of Pt (6.8 mA/g Pt) and superior power density (121 mW/cm2 at 90 °C) compared to commercially available carbon-supported catalysts. © Springer-Verlag Berlin Heidelberg 2014.

  7. Cobalt nanoparticle-embedded carbon nanotube/porous carbon hybrid derived from MOF-encapsulated Co3O4 for oxygen electrocatalysis.

    Science.gov (United States)

    Dou, Shuo; Li, Xingyue; Tao, Li; Huo, Jia; Wang, Shuangyin

    2016-08-11

    We successfully obtained a novel bi-functional electrocatalyst towards the ORR and OER: Co nanoparticle-embedded N-doped carbon nanotube (CNT)/porous carbon (PC) by pyrolyzing metal organic framework (MOF) encapsulated Co3O4. The as-obtained hybrid exhibited highly efficient electrocatalytic activity for the ORR and OER. Furthermore, the assembled Zn-air batteries also revealed promising performance and long-term stability. PMID:27411845

  8. A rare example of a porous Ca-MOF for the controlled release of biologically active NO.

    Science.gov (United States)

    Miller, Stuart R; Alvarez, Elsa; Fradcourt, Lucie; Devic, Thomas; Wuttke, Stefan; Wheatley, Paul S; Steunou, Nathalie; Bonhomme, Christian; Gervais, Christel; Laurencin, Danielle; Morris, Russell E; Vimont, Alexandre; Daturi, Marco; Horcajada, Patricia; Serre, Christian

    2013-09-14

    A 1D-microporous 3D calcium tetracarboxylate MOF has been solvothermally prepared and its structure solved from single crystal data. It exhibits coordinatively unsaturated Ca(2+) Lewis acid sites able to trap and deliver nitric oxide at a biological level.

  9. MOF nanoparticles coated by lipid bilayers and their uptake by cancer cells.

    Science.gov (United States)

    Wuttke, Stefan; Braig, Simone; Preiß, Tobias; Zimpel, Andreas; Sicklinger, Johannes; Bellomo, Claudia; Rädler, Joachim O; Vollmar, Angelika M; Bein, Thomas

    2015-11-11

    We report the synthesis of MOF@lipid nanoparticles as a versatile and powerful novel class of nanocarriers based on metal-organic frameworks (MOFs). We show that the MOF@lipid system can effectively store dye molecules inside the porous scaffold of the MOF while the lipid bilayer prevents their premature release. Efficient uptake of the MOF@lipid nanoparticles by cancer cells makes these nanocarriers promising for drug delivery and diagnostic purposes.

  10. Colorometric detection of water using MOF-polymer films and composites

    Science.gov (United States)

    Allendorf, Mark D.; Talin, Albert Alec

    2016-05-24

    A method including exposing a mixture of a porous metal organic framework (MOF) and a polymer to a predetermined molecular species, wherein the MOF has an open metal site for the predetermined molecular species and the polymer has a porosity for the predetermined molecular species; and detecting a color change of the MOF in the presence of the predetermined molecular species. A method including combining a porous metal organic framework (MOF) and a polymer, wherein the MOF has an open metal site for a predetermined molecular species and the polymer has a porosity for the predetermined molecular species. An article of manufacture including a mixture of a porous metal organic framework (MOF) and a polymer, wherein the MOF has an open metal site for a predetermined molecular species and the polymer has a porosity for the predetermined molecular species.

  11. MOF作模板制备多孔Au/CuxO催化剂及其CO氧化性能%MOF-templated preparation of porous Au/CuxO catalysts with octahedral structures for CO oxidation

    Institute of Scientific and Technical Information of China (English)

    刘朋飞; 张所瀛; 杨祝红; 陆小华

    2016-01-01

    采用MOF材料作模板,通过在Cu-BTC材料表面预先负载贵金属Au再热解的方法,成功制备了具有正八面体结构的新型多孔Au/CuxO负载型催化剂。通过降低热解环境中的O2浓度,调节氧化时间,实现了Au/Cu-BTC氧化产物组分的调节,分别制得了Au/Cu2O、Au/Cu2O-CuO、Au/CuO复合催化材料。将其用于CO催化氧化,发现所有Au/CuxO催化剂都表现出比Cu-BTC和Au/Cu-BTC更优异的催化性能,其中由于拥有较高的比表面积、Cu2O含量以及更好的Au的分散性,Au/Cu2O的CO氧化活性最佳,180℃即能实现CO的完全转化。%More recently, metal-organic frameworks (MOFs), as a excellent sacrificial template, have been widely used to fabricate a variety of porous metal oxides with special structures and performances. To take full advantage of MOFs in composition regulation, herein a novel method to prepare porous Au/CuxO composites with octahedral structures inherited from MOFs was introduced. Au/Cu-BTC was firstly prepared by the traditional deposition-precipitation method. Subsequently, pyrolysis of Au/Cu-BTC was conducted in 2% (volume fraction) O2 balanced with helium. By varying the time of heating, Au/CuxO composites including Au/Cu2O, Au/Cu2O-CuO and Au/CuO were successfully achieved. When tested in CO oxidation, these supported catalysts exhibited much better catalytic performances than Cu-BTC and Au/Cu-BTC due to the more active support of metal oxides. Thus, Au/Cu2O showed the best catalytic activity since the high surface area, Cu2O content and better dispersion of Au.

  12. Ligand flexibility and framework rearrangement in a new family of porous metal-organic frameworks

    DEFF Research Database (Denmark)

    Hawxwell, Samuel M; Espallargas, Guillermo Mínguez; Bradshaw, Darren;

    2007-01-01

    Ligand flexibility permits framework rearrangement upon evacuation and gas uptake in a new family of porous MOFs.......Ligand flexibility permits framework rearrangement upon evacuation and gas uptake in a new family of porous MOFs....

  13. Metal-Organic Framework (MOF) Compounds: Photocatalysts for Redox Reactions and Solar Fuel Production.

    Science.gov (United States)

    Dhakshinamoorthy, Amarajothi; Asiri, Abdullah M; García, Hermenegildo

    2016-04-25

    Metal-organic frameworks (MOFs) are crystalline porous materials formed from bi- or multipodal organic linkers and transition-metal nodes. Some MOFs have high structural stability, combined with large flexibility in design and post-synthetic modification. MOFs can be photoresponsive through light absorption by the organic linker or the metal oxide nodes. Photoexcitation of the light absorbing units in MOFs often generates a ligand-to-metal charge-separation state that can result in photocatalytic activity. In this Review we discuss the advantages and uniqueness that MOFs offer in photocatalysis. We present the best practices to determine photocatalytic activity in MOFs and for the deposition of co-catalysts. In particular we give examples showing the photocatalytic activity of MOFs in H2 evolution, CO2 reduction, photooxygenation, and photoreduction. PMID:26970539

  14. Stability of MOF-5 in a hydrogen gas environment containing fueling station impurities

    DEFF Research Database (Denmark)

    Ming, Yang; Purewal, Justin; Yang, Jun;

    2016-01-01

    Metal-organic frameworks (MOFs) are an emerging class of porous, crystalline materials with potential application as hydrogen storage media in fuel cell vehicles. Unlike lower capacity adsorbents such as zeolites and carbons, some MOFs are expected to degrade due to attack by impurities present...

  15. Nanoporous Transparent MOF Glasses with Accessible Internal Surface.

    Science.gov (United States)

    Zhao, Yingbo; Lee, Seung-Yul; Becknell, Nigel; Yaghi, Omar M; Angell, C Austen

    2016-08-31

    While glassy materials can be made from virtually every class of liquid (metallic, molecular, covalent, and ionic), to date, formation of glasses in which structural units impart porosity on the nanoscopic level remains undeveloped. In view of the well-established porosity of metal-organic frameworks (MOFs) and the flexibility of their design, we have sought to combine their formation principles with the general versatility of glassy materials. Although the preparation of glassy MOFs can be achieved by amorphization of crystalline frameworks, transparent glassy MOFs exhibiting permanent porosity accessible to gases are yet to be reported. Here, we present a generalizable chemical strategy for making such MOF glasses by assembly from viscous solutions of metal node and organic strut and subsequent evaporation of a plasticizer-modulator solvent. This process yields glasses with 300 m(2)/g internal surface area (obtained from N2 adsorption isotherms) and a 2 nm pore-pore separation. On a volumetric basis, this porosity (0.33 cm(3)/cm(3)) is 3 times that of the early MOFs (0.11 cm(3)/cm(3) for MOF-2) and within range of the most porous MOFs known (0.60 cm(3)/cm(3) for MOF-5). We believe the porosity originates from a 3D covalent network as evidenced by the disappearance of the glass transition signature as the solvent is removed and the highly cross-linked nanostructure builds up. Our work represents an important step forward in translating the versatility and porosity of MOFs to glassy materials.

  16. STUDY OF SYNTHESIS AND CHARACTERIZATION OF METAL-ORGANIC FRAMEWORKS MOF-5 AS HYDROGEN STORAGE MATERIAL

    Directory of Open Access Journals (Sweden)

    Prapti Rahayu

    2016-03-01

    Full Text Available Metal-organic frameworks (MOFs are porous coordination polymer containing bi-or polidentate organic linker coordinated with inorganic part, such as metal oxide cluster or metal cation as node which called as secondary building unit (SBU to form infinite structure. Due to high porosity and surface area, good thermal stability as well as the availability of unsaturated metal center or the linker influence attracts the interaction with gases, thus MOFs have potential to be applied as hydrogen storage material. One type of MOFs that have been widely studied is [Zn4O(benzene-1,4-dicarboxylate3], namely, MOF-5.Various synthesis method have been developed to obtain optimum results. Characterization of MOF-5 from various synthesis method such as crystallinity, capacity, stability, and quantum dot behavior of MOF-5 have been summarized in this review.

  17. MOF Crystal Chemistry Paving the Way to Gas Storage Needs: Aluminum Based soc-MOF for CH4, O2 and CO2 Storage

    KAUST Repository

    Alezi, Dalal

    2015-09-28

    The molecular building block approach was employed effectively to construct a series of novel isoreticular, highly porous and stable, aluminum based Metal-Organic Frameworks with soc topology. From this platform, three compounds were experimentally isolated and fully characterized, namely, the parent Al-soc-MOF-1 and its naphthalene and anthracene analogues. Al-soc-MOF-1 exhibits outstanding gravimetric methane uptake (total and working capacity). It is shown experimentally, for the first time, that the Al-soc-MOF platform can address the challenging Department of Energy dual target of 0.5 g/g (gravimetric) and 264 cm3 (STP)/cm3 (volumetric) methane storage. Furthermore, Al-soc-MOF exhibited the highest total gravimetric and volumetric uptake for carbon dioxide and the utmost total and deliverable uptake for oxygen at relatively high pressures among all microporous MOFs. In order to correlate the MOF pore structure and functionality to the gas storage properties, to better understand the structure-properties relationship, we performed a molecular simulation study and evaluated the methane storage performance of Al-soc-MOF platform using diverse organic linkers. It was found that shortening the parent Al-soc-MOF-1 linker resulted in a noticeable enhancement in the working volumetric capacity at specific temperatures and pressures with amply conserved gravimetric uptake/working capacity. In contrast, further expansion of the organic linker (branches and/or core) led to isostructural Al-soc-MOFs with enhanced gravimetric uptake but noticeably lower volumetric capacity. The collective experimental and simulation studies indicated that the parent Al-soc-MOF-1 exhibits the best compromise between the volumetric and gravimetric total and working uptakes in a wide range of pressure and temperature conditions.

  18. Design and Synthesis of a Water-Stable Anionic Uranium-Based Metal-Organic Framework (MOF) with Ultra Large Pores.

    Science.gov (United States)

    Li, Peng; Vermeulen, Nicolaas A; Gong, Xirui; Malliakas, Christos D; Stoddart, J Fraser; Hupp, Joseph T; Farha, Omar K

    2016-08-22

    Ionic metal-organic frameworks (MOFs) are a subclass of porous materials that have the ability to incorporate different charged species in confined nanospace by ion-exchange. To date, however, very few examples combining mesoporosity and water stability have been realized in ionic MOF chemistry. Herein, we report the rational design and synthesis of a water-stable anionic mesoporous MOF based on uranium and featuring tbo-type topology. The resulting tbo MOF exhibits exceptionally large open cavities (3.9 nm) exceeding those of all known anionic MOFs. By supercritical CO2 activation, a record-high Brunauer-Emmett-Teller (BET) surface area (2100 m(2)  g(-1) ) for actinide-based MOFs has been obtained. Most importantly, however, this new uranium-based MOF is water-stable and able to absorb positively charged ions selectively over negatively charged ones, enabling the efficient separation of organic dyes and biomolecules.

  19. Molecular simulation of polar molecules interaction with MOFs family materials

    International Nuclear Information System (INIS)

    The topic of this thesis is the adsorption of simple molecular fluids in nano-porous materials. Many industrial processes are based on this phenomenon, including ionic exchange, selective separation and heterogeneous catalysis. I used molecular simulation to study the adsorption properties of polar molecules of industrial interest (CO2 and H2O) in a new class of crystalline microporous hybrid organic-inorganic materials called Metal-Organic Frameworks (MOFs). They have exceptional adsorption properties due to their topological variety and their versatility, allowed by the large range of possibilities offered by organic and coordination chemistry and functionalizations. I first studied the adsorption of CO2 in a family of materials called IRMOFs, which share the same topology but have different porous volume, in order to characterize the effect of confinement on their adsorption performance. In particular, a general behavior has been highlighted: the critical temperature decreases when the confinement increases. Then, I looked at a recently synthesized cationic MOF called Zn2(CBTACN). After having localized the extra-framework halogen anions in the unit cell of the material, something which was not possible experimentally, I characterized CO2 adsorption in this system first as a pure gas and then as a component of different mixtures. Finally, I was interested in the hydrothermal stability of MOFs, a crucial issue for their use in industrial applications. I observed the hydration mechanism of system that is analogous to the MOF-5 (IRMOF-0h) and shed light on some collaborative effects of the attack of water that were unknown to in the literature. (author)

  20. MOF-derived, N-doped, hierarchically porous carbon sponges as immobilizers to confine selenium as cathodes for Li-Se batteries with superior storage capacity and perfect cycling stability

    Science.gov (United States)

    Li, Zhaoqiang; Yin, Longwei

    2015-05-01

    Nitrogen-doped carbon sponges (NCS) composed of hierarchical microporous carbon layers are derived from metal organic frameworks (MOFs) via carbonization at high temperatures under Ar and NH3 flow. Se is impregnated into 0.4-0.55 nm micropores by melting-diffusion and infiltration methods. The confinement of Se within small-sized micropores of NCS efficiently prevents Se loss, and mesopores between carbon layers absorb a sufficient amount of electrolyte, as well as serve as cushion spaces for large volume changes during delithiation-lithiation processes. Nitrogen doping improves the electrical conductivity of carbon matrix and facilitates rapid charge transfer, making the carbon sponge a highway for charges involved in redox reactions. When serving as cathode materials for Li-Se batteries, the NCS/Se-50 composite with 50 wt% Se exhibits excellent cycling stability, superior rate capability and high coulombic efficiency. The cathode can exhibit 443.2 mA h g-1 at the 200th cycle with a coulombic efficiency of up to 99.9% at 0.5C (C = 675 mA h g-1), which leads to 0.031% capacity loss per cycle from 5th to 200th cycles. Even at a high rate of 5C, it can still retain 286.6 mA h g-1. The unique, large surface rod-like MOF-derived, N-doped carbon sponges with hierarchical porosity could be potential candidates in the related energy-storage systems.Nitrogen-doped carbon sponges (NCS) composed of hierarchical microporous carbon layers are derived from metal organic frameworks (MOFs) via carbonization at high temperatures under Ar and NH3 flow. Se is impregnated into 0.4-0.55 nm micropores by melting-diffusion and infiltration methods. The confinement of Se within small-sized micropores of NCS efficiently prevents Se loss, and mesopores between carbon layers absorb a sufficient amount of electrolyte, as well as serve as cushion spaces for large volume changes during delithiation-lithiation processes. Nitrogen doping improves the electrical conductivity of carbon matrix and

  1. Novel Applications for Oxalate-Phosphate-Amine Metal-Organic-Frameworks (OPA-MOFs): Can an Iron-Based OPA-MOF Be Used as Slow-Release Fertilizer?

    Science.gov (United States)

    Anstoetz, Manuela; Rose, Terry J; Clark, Malcolm W; Yee, Lachlan H; Raymond, Carolyn A; Vancov, Tony

    2015-01-01

    A porous iron-based oxalate-phosphate-amine metal-organic framework material (OPA-MOF) was investigated as a microbially-induced slow-release nitrogen (N) and phosphorus (P) fertilizer. Seedling growth, grain yields, nutrient uptake of wheat plants, and soil dynamics in incubated soil, were investigated using OPA-MOF vs standard P (triple-superphosphate) and N (urea) fertilizers in an acidic Ferralsol at two application rates (equivalent 120 and 40 kg N ha(-1)). While urea hydrolysis in the OPA-MOF treatment was rapid, conversion of ammonium to nitrate was significantly inhibited compared to urea treatment. Reduced wheat growth in OPA-MOF treatments was not caused by N-deficiency, but by limited P-bioavailability. Two likely reasons were slow P-mobilisation from the OPA-MOF or rapid P-binding in the acid soil. P-uptake and yield in OPA-MOF treatments were significantly higher than in nil-P controls, but significantly lower than in conventionally-fertilised plants. OPA-MOF showed potential as enhanced efficiency N fertilizer. However, as P-bioavailability was insufficient to meet plant demands, further work should determine if P-availability may be enhanced in alkaline soils, or whether central ions other than Fe, forming the inorganic metal-P framework in the MOF, may act as a more effective P-source in acid soils. PMID:26633174

  2. Novel Applications for Oxalate-Phosphate-Amine Metal-Organic-Frameworks (OPA-MOFs): Can an Iron-Based OPA-MOF Be Used as Slow-Release Fertilizer?

    Science.gov (United States)

    Anstoetz, Manuela; Rose, Terry J; Clark, Malcolm W; Yee, Lachlan H; Raymond, Carolyn A; Vancov, Tony

    2015-01-01

    A porous iron-based oxalate-phosphate-amine metal-organic framework material (OPA-MOF) was investigated as a microbially-induced slow-release nitrogen (N) and phosphorus (P) fertilizer. Seedling growth, grain yields, nutrient uptake of wheat plants, and soil dynamics in incubated soil, were investigated using OPA-MOF vs standard P (triple-superphosphate) and N (urea) fertilizers in an acidic Ferralsol at two application rates (equivalent 120 and 40 kg N ha(-1)). While urea hydrolysis in the OPA-MOF treatment was rapid, conversion of ammonium to nitrate was significantly inhibited compared to urea treatment. Reduced wheat growth in OPA-MOF treatments was not caused by N-deficiency, but by limited P-bioavailability. Two likely reasons were slow P-mobilisation from the OPA-MOF or rapid P-binding in the acid soil. P-uptake and yield in OPA-MOF treatments were significantly higher than in nil-P controls, but significantly lower than in conventionally-fertilised plants. OPA-MOF showed potential as enhanced efficiency N fertilizer. However, as P-bioavailability was insufficient to meet plant demands, further work should determine if P-availability may be enhanced in alkaline soils, or whether central ions other than Fe, forming the inorganic metal-P framework in the MOF, may act as a more effective P-source in acid soils.

  3. Novel Applications for Oxalate-Phosphate-Amine Metal-Organic-Frameworks (OPA-MOFs: Can an Iron-Based OPA-MOF Be Used as Slow-Release Fertilizer?

    Directory of Open Access Journals (Sweden)

    Manuela Anstoetz

    Full Text Available A porous iron-based oxalate-phosphate-amine metal-organic framework material (OPA-MOF was investigated as a microbially-induced slow-release nitrogen (N and phosphorus (P fertilizer. Seedling growth, grain yields, nutrient uptake of wheat plants, and soil dynamics in incubated soil, were investigated using OPA-MOF vs standard P (triple-superphosphate and N (urea fertilizers in an acidic Ferralsol at two application rates (equivalent 120 and 40 kg N ha(-1. While urea hydrolysis in the OPA-MOF treatment was rapid, conversion of ammonium to nitrate was significantly inhibited compared to urea treatment. Reduced wheat growth in OPA-MOF treatments was not caused by N-deficiency, but by limited P-bioavailability. Two likely reasons were slow P-mobilisation from the OPA-MOF or rapid P-binding in the acid soil. P-uptake and yield in OPA-MOF treatments were significantly higher than in nil-P controls, but significantly lower than in conventionally-fertilised plants. OPA-MOF showed potential as enhanced efficiency N fertilizer. However, as P-bioavailability was insufficient to meet plant demands, further work should determine if P-availability may be enhanced in alkaline soils, or whether central ions other than Fe, forming the inorganic metal-P framework in the MOF, may act as a more effective P-source in acid soils.

  4. Versatile Rare Earth Hexanuclear Clusters for the Design and Synthesis of Highly-connected ftw-MOFs

    KAUST Repository

    Eddaoudi, Mohamed

    2015-04-15

    A series of highly porous MOFs were deliberately targeted to contain a 12-connected rare earth hexanuclear cluster and quadrangular tetracarboxylate ligands. The resultant MOFs have an underlying topology of ftw, (4, 12)-c ftw-MOFs. This targeted RE ftw-MOF platform offers potential to assess the effect of pore functionality and size, via ligand functionalization and/or expansion, on adsorption properties of relevant gases. Examination of gas adsorption properties of these compounds showed that the ftw-MOF-2 analogues, constructed from rigid ligands having a phenyl, a naphthyl or an anthracene core, exhibited a relatively high degree of porosity. The specific surface areas and pore volumes of these analogs are amongst the highest reported for rare earth based MOFs. Further studies reveal that Y-ftw-MOF-2 shows promising attributes as a storage media for methane (CH4) at high pressures. Furthermore, Y-ftw-MOF-2 shows potential as a separation agent for the selective removal of normal butane (n-C4H10) and propane (C3H8) from natural gas (NG) as well as interesting properties for the selective separation of n-C4H10 from C3H8 or isobutane (iso-C4H10).

  5. MOF-5-Polystyrene: Direct Production from Monomer, Improved Hydrolytic Stability, and Unique Guest Adsorption.

    Science.gov (United States)

    Gamage, Nipuni-Dhanesha H; McDonald, Kyle A; Matzger, Adam J

    2016-09-19

    An unprecedented mode of reactivity of Zn4 O-based metal-organic frameworks (MOFs) offers a straightforward and powerful approach to polymer-hybridized porous solids. The concept is illustrated with the production of MOF-5-polystyrene wherein polystyrene is grafted and uniformly distributed throughout MOF-5 crystals after heating in pure styrene for 4-24 h. The surface area and polystyrene content of the material can be fine-tuned by controlling the duration of heating styrene in the presence of MOF-5. Polystyrene grafting significantly alters the physical and chemical properties of pristine MOF-5, which is evident from the unique guest adsorption properties (solvatochromic dye uptake and improved CO2 capacity) as well as the dramatically improved hydrolytic stability of composite. Based on the fact that MOF-5 is the best studied member of the structure class, and has been produced at scale by industry, these findings can be directly leveraged for a range of current applications.

  6. MOF-5-Polystyrene: Direct Production from Monomer, Improved Hydrolytic Stability, and Unique Guest Adsorption.

    Science.gov (United States)

    Gamage, Nipuni-Dhanesha H; McDonald, Kyle A; Matzger, Adam J

    2016-09-19

    An unprecedented mode of reactivity of Zn4 O-based metal-organic frameworks (MOFs) offers a straightforward and powerful approach to polymer-hybridized porous solids. The concept is illustrated with the production of MOF-5-polystyrene wherein polystyrene is grafted and uniformly distributed throughout MOF-5 crystals after heating in pure styrene for 4-24 h. The surface area and polystyrene content of the material can be fine-tuned by controlling the duration of heating styrene in the presence of MOF-5. Polystyrene grafting significantly alters the physical and chemical properties of pristine MOF-5, which is evident from the unique guest adsorption properties (solvatochromic dye uptake and improved CO2 capacity) as well as the dramatically improved hydrolytic stability of composite. Based on the fact that MOF-5 is the best studied member of the structure class, and has been produced at scale by industry, these findings can be directly leveraged for a range of current applications. PMID:27555362

  7. Crystallography of Representative MOFs Based on Pillared Cyanonickelate (PICNIC Architecture

    Directory of Open Access Journals (Sweden)

    Winnie Wong-Ng

    2016-09-01

    Full Text Available The pillared layer motif is a commonly used route to porous coordination polymers or metal organic frameworks (MOFs. Materials based on the pillared cyano-bridged architecture, [Ni’(LNi(CN4]n (L = pillar organic ligands, also known as PICNICs, have been shown to be especially diverse where pore size and pore functionality can be varied by the choice of pillar organic ligand. In addition, a number of PICNICs form soft porous structures that show reversible structure transitions during the adsorption and desorption of guests. The structural flexibility in these materials can be affected by relatively minor differences in ligand design, and the physical driving force for variations in host-guest behavior in these materials is still not known. One key to understanding this diversity is a detailed investigation of the crystal structures of both rigid and flexible PICNIC derivatives. This article gives a brief review of flexible MOFs. It also reports the crystal structures of five PICNICS from our laboratories including three 3-D porous frameworks (Ni-Bpene, NI-BpyMe, Ni-BpyNH2, one 2-D layer (Ni-Bpy, and one 1-D chain (Ni-Naph compound. The sorption data of BpyMe for CO2, CH4 and N2 is described. The important role of NH3 (from the solvent of crystallization as blocking ligands which prevent the polymerization of the 1-D chains and 2-D layers to become 3D porous frameworks in the Ni-Bpy and Ni-Naph compounds is also addressed.

  8. Geometrical Properties Can Predict CO2 and N2 Adsorption Performance of Metal-Organic Frameworks (MOFs) at Low Pressure.

    Science.gov (United States)

    Fernandez, Michael; Barnard, Amanda S

    2016-05-01

    Metal-organic frameworks (MOFs) are nanoporous materials with exceptional host-guest properties poised for groundbreaking innovations in gas separation applications according to high-throughput (HT) screening data. However, MOF structural libraries are nearly infinite in practice and so statistical and information technology will play a fundamental role in implementing and rationalizing MOF virtual screening. In this work, we apply k-means clustering and archetypal analysis (AA) to identify the truly significant nanoporous structures in a large library of ∼82 000 virtual MOFs. Quantitative structure-property relationship (QSPR) models of the theoretical CO2 and N2 uptake capacities were also developed using a calibration set of ∼16 000 hypothetical MOF structures derived from the prototypes and archetype frameworks. Since uptake capacities correlated poorly to the void fraction, surface area and pore size but these properties were used to build binary classifier predictors that successfully identify "high-performing" nanoporous materials in an external test set of ∼65 000 MOFs with accuracy higher than 94%. The accuracy of the classification decreased for MOFs with fluorine substituents. The classification models can serve as efficient filtering tools to detecting promising high-performing candidates at the early stage of virtual high-throughput screening of novel porous materials. PMID:27022760

  9. Interplay of metalloligand and organic ligand to tune micropores within isostructural mixed-metal organic frameworks (M'MOFs) for their highly selective separation of chiral and achiral small molecules

    NARCIS (Netherlands)

    M. C. Das; Q. Guo; Y. He; J. Kim; C.-G. Zhao; K. Hong; S. Xiang; Z. Zhang; K. M. Thomas; R. Krishna; B. Chen

    2012-01-01

    Four porous isostructural mixed-metal-organic frameworks (M′MOFs) have been synthesized and structurally characterized. The pores within these M′MOFs are systematically tuned by the interplay of both the metalloligands and organic ligands which have enabled us not only to direct their highly selecti

  10. Influence of metal doping of a MOF-74 framework on hydrogen adsorption

    Energy Technology Data Exchange (ETDEWEB)

    Botas, J.A.; Calleja, G.; Orcajo, M.G. [Rey Juan Carlos Univ., Madrid (Spain). Dept. of Chemical and Energy Technology; Sanchez-Sanchez, M. [CSIC, Madrid (Spain). Inst. de Catalisis y Petroleoquimica

    2010-07-01

    Microporous Metal-Organic Framework (MOF) adsorbents are considered an interesting option for hydrogen storage. Due to their porous nature and unusually high surface areas, these materials show an exceptional H{sub 2} uptake. Unfortunately, their interaction with H{sub 2} molecules is weak, so cryogenic temperatures are required to reach competitive H{sub 2} storage capacities. In this sense, the presence of coordinatively unsaturated and exposed metal centers in some MOF frameworks could increase the affinity for H{sub 2} through stronger metal-H{sub 2} interactions. In this preliminary work, the effect of doping a Zn{sup 2+}-MOF-74 framework with Co{sup 2+}, Cu{sup 2+} and Mg{sup 2+} on its adsorption properties for H{sub 2} has been studied. Characterization studies suggest that the samples prepared have actually the MOF-74 structure, in which the different tested heteroatom ions have been successfully incorporated. The differences in H{sub 2} adsorption at 77 K and 87 K between the MOF-74 samples doped with the mentioned divalent metal ions were discussed as a function of their free pore volume and amount of metal incorporation. (orig.)

  11. Co(II)-doped MOF-5 nano/microcrystals: Solvatochromic behaviour, sensing solvent molecules and gas sorption property

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Ji-Min [Coordination Chemistry Institute, State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing National Laboratory of Microstructures, Nanjing University, Nanjing 210093 (China); School of Chemistry and Chemical Engineering, Linyi University, Linyi 276005 (China); Liu, Qing [Coordination Chemistry Institute, State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing National Laboratory of Microstructures, Nanjing University, Nanjing 210093 (China); Sun, Wei-Yin, E-mail: sunwy@nju.edu.cn [Coordination Chemistry Institute, State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing National Laboratory of Microstructures, Nanjing University, Nanjing 210093 (China)

    2014-10-15

    Co(II)-doped MOF-5 nano/microcrystals with controllable morphology and size were successfully obtained by solvothermal method. The products were characterized by powder X-ray diffraction (PXRD), energy dispersive spectrometry (EDS), field emission scanning electron microscopy (FESEM), thermogravimetric analysis (TGA), inductively coupled plasma optical emission spectrometer (ICP-OES), elemental analysis, UV–vis and infrared (IR) spectroscopy. The factors influencing the crystal morphology and size were investigated. The gas sorption measurements reveal that highly crystalline particles have large Langmuir surface area. It was found that the Co(II)-doped MOF-5 shows enhanced hydrostability and the sorption profiles of the Co(II)-doped MOF-5 nano/microcrystals are dependent on the morphology and size of the particles. Porous Co(II)-doped MOF-5 is stable upon the removal of guest molecules and exhibits different colour with accommodating different solvent molecule, which means that it can act as solvatochromic sensing materials for recognition of solvent molecules. - Graphical abstract: Co(II)-doped MOF-5 nano/microcrystals with different shapes and sizes were synthesized by a facile hydrothermal method, which not only enhance gas sorption properties and structural stability of MOFs towards moisture, but also act as new sensing materials for sensing small molecules. - Highlights: • Co(II)-doped MOF-5 nano/microcrystals with controllable morphology and size were obtained. • Co(II)-doped MOF-5 nano/microcrystals enhance the structural stability towards moisture. • Co(II)-doped MOF-5 can act as new sensing material for sensing small molecules.

  12. Transforming MOFs for Energy Applications Using the Guest@MOF Concept.

    Science.gov (United States)

    Ullman, Andrew M; Brown, Jonathan W; Foster, Michael E; Léonard, François; Leong, Kirsty; Stavila, Vitalie; Allendorf, Mark D

    2016-08-01

    As the world transitions from fossil fuels to clean energy sources in the coming decades, many technological challenges will require chemists and material scientists to develop new materials for applications related to energy conversion, storage, and efficiency. Because of their unprecedented adaptability, metal-organic frameworks (MOFs) will factor strongly in this portfolio. By utilizing the broad synthetic toolkit provided by the fields of organic and inorganic chemistry, MOF pores can be customized to suit a particular application. Of particular importance is the ability to tune the strength of the interaction between the MOF pores and guest molecules. By cleverly controlling these MOF-guest interactions, the chemist may impart new function into the Guest@MOF materials otherwise lacking in vacant MOF. Herein, we highlight the concept of the Guest@MOF as it relates to our efforts to develop these materials for energy-related applicatons. Our work in the areas of H2 and noble gas storage, hydrogenolysis of biomass, light-harvesting, and conductive materials will be discussed. Of relevance to light-harvesting applications, we report for the first time a postsynthetic modification strategy for increasing the loading of a light-sensitive electron-donor molecule in the pores of a functionalized MIL-101 structure. Through the demonstrated versatility of these approaches, we show that, by treating guest molecules as integral design elements for new MOF constructs, MOF science can have a significant impact on the advancement of clean energy technologies.

  13. Transforming MOFs for Energy Applications Using the Guest@MOF Concept.

    Science.gov (United States)

    Ullman, Andrew M; Brown, Jonathan W; Foster, Michael E; Léonard, François; Leong, Kirsty; Stavila, Vitalie; Allendorf, Mark D

    2016-08-01

    As the world transitions from fossil fuels to clean energy sources in the coming decades, many technological challenges will require chemists and material scientists to develop new materials for applications related to energy conversion, storage, and efficiency. Because of their unprecedented adaptability, metal-organic frameworks (MOFs) will factor strongly in this portfolio. By utilizing the broad synthetic toolkit provided by the fields of organic and inorganic chemistry, MOF pores can be customized to suit a particular application. Of particular importance is the ability to tune the strength of the interaction between the MOF pores and guest molecules. By cleverly controlling these MOF-guest interactions, the chemist may impart new function into the Guest@MOF materials otherwise lacking in vacant MOF. Herein, we highlight the concept of the Guest@MOF as it relates to our efforts to develop these materials for energy-related applicatons. Our work in the areas of H2 and noble gas storage, hydrogenolysis of biomass, light-harvesting, and conductive materials will be discussed. Of relevance to light-harvesting applications, we report for the first time a postsynthetic modification strategy for increasing the loading of a light-sensitive electron-donor molecule in the pores of a functionalized MIL-101 structure. Through the demonstrated versatility of these approaches, we show that, by treating guest molecules as integral design elements for new MOF constructs, MOF science can have a significant impact on the advancement of clean energy technologies. PMID:27399607

  14. Advanced fabrication method for the preparation of MOF thin films: Liquid-phase epitaxy approach meets spin coating method.

    KAUST Repository

    Chernikova, Valeriya

    2016-07-14

    Here we report a new and advanced method for the fabrication of highly oriented/polycrystalline metal-organic framework (MOF) thin films. Building on the attractive features of the liquid-phase epitaxy (LPE) approach, a facile spin coating method was implemented to generate MOF thin films in a high-throughput fashion. Advantageously, this approach offers a great prospective to cost-effectively construct thin-films with a significantly shortened preparation time and a lessened chemicals and solvents consumption, as compared to the conventional LPE-process. Certainly, this new spin-coating approach has been implemented successfully to construct various MOF thin films, ranging in thickness from a few micrometers down to the nanometer scale, spanning 2-D and 3-D benchmark MOF materials including Cu2(bdc)2•xH2O, Zn2(bdc)2•xH2O, HKUST-1 and ZIF-8. This method was appraised and proved effective on a variety of substrates comprising functionalized gold, silicon, glass, porous stainless steel and aluminum oxide. The facile, high-throughput and cost-effective nature of this approach, coupled with the successful thin film growth and substrate versatility, represents the next generation of methods for MOF thin film fabrication. Thereby paving the way for these unique MOF materials to address a wide range of challenges in the areas of sensing devices and membrane technology.

  15. Novel Applications for Oxalate-Phosphate-Amine Metal-Organic-Frameworks (OPA-MOFs): Can an Iron-Based OPA-MOF Be Used as Slow-Release Fertilizer?

    OpenAIRE

    Manuela Anstoetz; Rose, Terry J.; Clark, Malcolm W.; Yee, Lachlan H.; Raymond, Carolyn A.; Tony Vancov

    2015-01-01

    A porous iron-based oxalate-phosphate-amine metal-organic framework material (OPA-MOF) was investigated as a microbially-induced slow-release nitrogen (N) and phosphorus (P) fertilizer. Seedling growth, grain yields, nutrient uptake of wheat plants, and soil dynamics in incubated soil, were investigated using OPA-MOF vs standard P (triple-superphosphate) and N (urea) fertilizers in an acidic Ferralsol at two application rates (equivalent 120 and 40 kg N ha(-1)). While urea hydrolysis in the O...

  16. Dynamics of Bloch State Positronium Emission from MOF Targets Studied via Rydberg TOF Spectroscopy

    Science.gov (United States)

    Piñeiro Escalera, Alina; Jones, Adric; Mills, Allen

    2016-05-01

    Recent advances in the efficient production and detection of Rydberg positronium (Ps) have made it possible to perform energy- and angle- resolved time-of-flight (TOF) spectroscopy with Ps. We report here TOF measurements of Ps emission from the metal-oxide framework (MOF) targets, MOF-5 and ZIF-8. MOFs are a recently synthesized class of chemical structures, characterized by high long-range order and large surface area to volume ratios (i.e., they are highly porous and uniform, crystalline materials). Ps is found to be emitted predominantly in a series of monoenergetic peaks, providing clear evidence of Ps Bloch states. Measuring the relative populations of the monoenergetic peaks, as a function of implantation energy and target temperature, provides insight into the target-dependent dynamics of Bloch state Ps. Work supported by the U.S. National Science Foundation Grants No. PHY 1206100 and No. PHY 1040590 and the National Science Foundation Graduate Research Fellowship Progam (NSF-GRFP). DOE BES DE-FG02-13ER46972 (MOF-5 synthesis and characterization).

  17. NMR studies of benzene mobility in microporous metal-organic framework MOF-5

    International Nuclear Information System (INIS)

    Microporous metal-organic frameworks (MOF) are crystalline coordination polymers with regular three dimensional pore networks. These pore networks enable adsorption and diffusion of guest molecules. Molecular Dynamics (MD) simulations show that benzene has a liquid-like mobility inside the pores of MOF-5. Nuclear Magnetic Resonance (NMR) methods allow experimental access to guest mobilities inside such pore networks. This report presents the results of pulsed field gradient NMR (PFG NMR) self-diffusion measurements of benzene adsorbed in MOF-5. In these experiments multi-exponential spin echo decays were observed, which are usually caused by different phases of self-diffusion. These different phases of benzene mobility were unexpected for diffusion of molecules inside an isotropic framework and have to originate in the host-guest and guest-guest interaction. By modern diffusion-relaxation correlation spectroscopy (DRCOSY) translational self-diffusion and microscopic relaxation behavior were correlated. Together with magic angle spinning (MAS) NMR spectroscopy these investigations reveal that the faster component of the diffusion coefficients can be assigned to diffusion inside the porous crystal structure of MOF-5.

  18. Performance and plasticization behavior of polymer–MOF membranes for gas separation at elevated pressures

    NARCIS (Netherlands)

    Shahid, Salman; Nijmeijer, Kitty

    2014-01-01

    Mixed matrix membranes (MMMs) based on three distinctively different MOFs (MIL-53(Al) (breathing MOF), ZIF-8 (flexible MOF) and Cu3BTC2 (rigid MOF)) dispersed in Matrimid®-PI have been investigated. MOF loading was varied between 0 wt% and 30 wt%. The fabricated MOF-MMMs were characterized for pure

  19. Structure-property relationship of metal-organic frameworks (MOFs) and physisorbed off-gas radionuclides

    International Nuclear Information System (INIS)

    We report on the host-guest interactions between metal-organic frameworks (MOFs) with various profiles and highly polarizable molecules (iodine), with emphasis on identifying preferential sorption sites in these systems. Radioactive iodine 129I, along with other volatile radionuclides (3H, 14C, Xe and Kr), represents a relevant component in the off-gas resulted during nuclear fuel reprocessing. Due to its very long half-life, 15.7 x 106 years, and potential health risks in humans, its efficient capture and long-term storage is of great importance. The leading iodine capture technology to date is based on trapping iodine in silver-exchanged mordenite. Our interests are directed towards improving existent capturing technologies, along with developing novel materials and alternative waste forms. Herein we report the first study that systematically monitors iodine loading onto MOFs, an emerging new class of porous solid-state materials. In this context, MOFs are of particular interest as: (i) they serve as ideal high capacity storage media, (ii) they hold potential for the selective adsorption from complex streams, due to their high versatility and tunability. This work highlights studies on both newly developed in our lab, and known highly porous MOFs that all possess distinct characteristics (specific surface area, pore volume, pore size, and dimension of the window access to the pore). The materials were loaded to saturation, where elemental iodine was introduced from solution, as well as from vapor phase. Uptakes in the range of ∼125-150 wt% I2 sorbed were achieved, indicating that these materials outperform all other solid adsorbents to date in terms of overall capacity. Additionally, the loaded materials can be efficiently encapsulated in stable waste forms, including as low temperature sintering glasses. Ongoing studies are focused on gathering qualitative information with respect to localizing the physisorbed iodine molecules within the frameworks: X

  20. Structure-property relationship of metal-organic frameworks (MOFs) and physisorbed off-gas radionuclides.

    Energy Technology Data Exchange (ETDEWEB)

    Nenoff, Tina Maria; Chupas, Peter J. (Argonne National Laboratory); Garino, Terry J.; Rodriguez, Mark Andrew; Chapman, Karena W. (Argonne National Laboratory); Sava, Dorina Florentina

    2010-11-01

    We report on the host-guest interactions between metal-organic frameworks (MOFs) with various profiles and highly polarizable molecules (iodine), with emphasis on identifying preferential sorption sites in these systems. Radioactive iodine 129I, along with other volatile radionuclides (3H, 14C, Xe and Kr), represents a relevant component in the off-gas resulted during nuclear fuel reprocessing. Due to its very long half-life, 15.7 x 106 years, and potential health risks in humans, its efficient capture and long-term storage is of great importance. The leading iodine capture technology to date is based on trapping iodine in silver-exchanged mordenite. Our interests are directed towards improving existent capturing technologies, along with developing novel materials and alternative waste forms. Herein we report the first study that systematically monitors iodine loading onto MOFs, an emerging new class of porous solid-state materials. In this context, MOFs are of particular interest as: (i) they serve as ideal high capacity storage media, (ii) they hold potential for the selective adsorption from complex streams, due to their high versatility and tunability. This work highlights studies on both newly developed in our lab, and known highly porous MOFs that all possess distinct characteristics (specific surface area, pore volume, pore size, and dimension of the window access to the pore). The materials were loaded to saturation, where elemental iodine was introduced from solution, as well as from vapor phase. Uptakes in the range of {approx}125-150 wt% I2 sorbed were achieved, indicating that these materials outperform all other solid adsorbents to date in terms of overall capacity. Additionally, the loaded materials can be efficiently encapsulated in stable waste forms, including as low temperature sintering glasses. Ongoing studies are focused on gathering qualitative information with respect to localizing the physisorbed iodine molecules within the frameworks: X

  1. Remarkable Improvement in the Mechanical Properties and CO2 Uptake of MOFs Brought About by Covalent Linking to Graphene.

    Science.gov (United States)

    Kumar, Ram; Raut, Devaraj; Ramamurty, Upadrasta; Rao, C N R

    2016-06-27

    Metal-organic frameworks (MOFs) are exceptional as gas adsorbents but their mechanical properties are poor. We present a successful strategy to improve the mechanical properties along with gas adsorption characteristics, wherein graphene (Gr) is covalently bonded with M/DOBDC (M=Mg(2+) , Ni(2+) , or Co(2+) , DOBDC=2,5-dioxido-1,4-benzene dicarboxylate) MOFs. The surface area of the graphene-MOF composites increases up to 200-300 m(2)  g(-1) whereas the CO2 uptake increases by ca. 3-5 wt % at 0.15 atm and by 6-10 wt % at 1 atm. What is significant is that the composites exhibit improved mechanical properties. In the case of Mg/DOBDC, a three-fold increase in both the elastic modulus and hardness with 5 wt % graphene reinforcement is observed. Improvement in both the mechanical properties and gas adsorption characteristics of porous MOFs on linking them to graphene is a novel observation and suggests a new avenue for the design and synthesis of porous materials. PMID:27282430

  2. Study of the incorporation and release of the non-conventional half-sandwich ruthenium(II) metallodrug RAPTA-C on a robust MOF.

    Science.gov (United States)

    Procopio, Elsa Quartapelle; Rojas, Sara; Padial, Natalia M; Galli, Simona; Masciocchi, Norberto; Linares, Fátima; Miguel, Delia; Oltra, J Enrique; Navarro, Jorge A R; Barea, Elisa

    2011-11-14

    The highly porous and robust [Ni(8)(OH)(4)(OH(2))(2)(4,4'-(buta-1,3-diyne-1,4-diyl)bispyrazolato)(6)](n) MOF can be used as a proof of concept for the incorporation and release of the non-conventional [Ru(p-cymene)Cl(2)(pta)] RAPTA-C metallodrug. PMID:21952589

  3. Reticular Chemistry at Its Best: Directed Assembly of Hexagonal Building Units into the Awaited Metal-Organic Framework with the Intricate Polybenzene Topology, pbz-MOF

    KAUST Repository

    Alezi, Dalal

    2016-10-05

    The ability to direct the assembly of hexagonal building units offers great prospective to construct the awaited and looked-for hypothetical polybenzene (pbz) or “cubic graphite” structure, described 70 years ago. Here, we demonstrate the successful use of reticular chemistry as an appropriate strategy for the design and deliberate construction of a zirconium-based metal–organic framework (MOF) with the intricate pbz underlying net topology. The judicious selection of the perquisite hexagonal building units, six connected organic and inorganic building blocks, allowed the formation of the pbz-MOF-1, the first example of a Zr(IV)-based MOF with pbz topology. Prominently, pbz-MOF-1 is highly porous, with associated pore size and pore volume of 13 Å and 0.99 cm3 g–1, respectively, and offers high gravimetric and volumetric methane storage capacities (0.23 g g–1 and 210.4 cm3 (STP) cm–3 at 80 bar). Notably, the pbz-MOF-1 pore system permits the attainment of one of the highest CH4 adsorbed phase density enhancements at high pressures (0.15 and 0.21 g cm–3 at 35 and 65 bar, respectively) as compared to benchmark microporous MOFs.

  4. Quest for Highly-connected MOF Platforms: Rare-Earth Polynuclear Clusters Versatility Meets Net Topology Needs.

    KAUST Repository

    Alezi, Dalal

    2015-04-07

    Gaining control over the assembly of highly porous rare-earth (RE) based metal-organic frameworks (MOFs) remains challenging. Here we report the latest discoveries on our continuous quest for highly-connected nets. The topological exploration based on the non-compatibility of 12-connected RE polynuclear carboxylate-based cluster, points of extension matching the 12 vertices of the cuboctahedron (cuo), with 3-connected organic ligands led to the discovery of two fascinating and highly-connected minimal edge-transitive nets, pek and aea. The reduced symmetry of the employed triangular tricarboxylate ligand, as compared to the prototype highly symmetrical 1,3,5-benzene(tris)benzoic acid guided the concurrent occurrence of nonanuclear [RE9(μ3-OH)12(μ3-O)2(O2C–)12] and hexanuclear [RE6(OH)8(O2C–)8] carboxylate-based clusters as 12-connected and 8-connected molecular building blocks in the structure of a 3-periodic pek-MOF based on a novel (3,8,12)-c trinodal net. The use of a tricarboxylate ligand with modified angles between carboxylate moieties led to the formation of a second MOF containing solely nonanuclear clusters and exhibiting once more a novel and a highly-connected (3,12,12)-c trinodal net with aea topology. Notably, it is the first time that RE-MOFs with double six-membered ring (d6R) secondary building units are isolated, representing therefore a critical step forward toward the design of novel and highly coordinated materials using the supermolecular building layer approach while considering the d6Rs as building pillars. Lastly, the potential of these new MOFs for gas separation/storage was investigated by performing gas adsorption studies of various probe gas molecules over a wide range of pressures. Noticeably, pek-MOF-1 showed excellent volumetric CO2 and CH4 uptakes at high pressures.

  5. Simulation and Modelling of MOFs for Hydrogen Storage

    OpenAIRE

    Başdoğan, Yasemin; Keskin Avcı, Seda

    2015-01-01

    Metal organic frameworks (MOFs) have received significant attention in recent years both from academia and industry since this new class of nanoporous materials has many potential advantages over traditional nanoporous materials in gas storage and separation applications. Hydrogen storage has been one of the most widely investigated applications of MOFs and recent experimental studies have shown that several MOFs are promising for hydrogen storage at low temperatures and moderate pressures. I...

  6. MOF-based electronic and opto-electronic devices.

    Science.gov (United States)

    Stavila, V; Talin, A A; Allendorf, M D

    2014-08-21

    Metal-organic frameworks (MOFs) are a class of hybrid materials with unique optical and electronic properties arising from rational self-assembly of the organic linkers and metal ions/clusters, yielding myriads of possible structural motifs. The combination of order and chemical tunability, coupled with good environmental stability of MOFs, are prompting many research groups to explore the possibility of incorporating these materials as active components in devices such as solar cells, photodetectors, radiation detectors, and chemical sensors. Although this field is only in its incipiency, many new fundamental insights relevant to integrating MOFs with such devices have already been gained. In this review, we focus our attention on the basic requirements and structural elements needed to fabricate MOF-based devices and summarize the current state of MOF research in the area of electronic, opto-electronic and sensor devices. We summarize various approaches to designing active MOFs, creation of hybrid material systems combining MOFs with other materials, and assembly and integration of MOFs with device hardware. Critical directions of future research are identified, with emphasis on achieving the desired MOF functionality in a device and establishing the structure-property relationships to identify and rationalize the factors that impact device performance. PMID:24802763

  7. Molecularly Imprinted Polymer (MIP) Film with Improved Surface Area Developed by Using Metal-Organic Framework (MOF) for Sensitive Lipocalin (NGAL) Determination.

    Science.gov (United States)

    Iskierko, Zofia; Sharma, Piyush Sindhu; Prochowicz, Daniel; Fronc, Krzysztof; D'Souza, Francis; Toczydłowska, Diana; Stefaniak, Filip; Noworyta, Krzysztof

    2016-08-10

    Electropolymerizable functional and cross-linking monomers were used to prepare conducting molecularly imprinted polymer film with improved surface area with the help of a sacrificial metal-organic framework (MOF). Subsequent dissolution of the MOF layer resulted in a surface developed MIP film. This surface enlargement increased the analyte accessibility to imprinted molecular cavities. Application of the porous MIP film as a recognition unit of an extended-gate field effect transistor (EG-FET) chemosensor effectively enhanced analytical current signals of determination of recombinant human neutrophil gelatinase-associated lipocalin (NGAL). PMID:27454556

  8. Single-Crystal-to-Single-Crystal Anion Exchange in a Gadolinium MOF: Incorporation of POMs and [AuCl4]−

    Directory of Open Access Journals (Sweden)

    Javier López-Cabrelles

    2016-04-01

    Full Text Available The encapsulation of functional molecules inside porous coordination polymers (also known as metal-organic frameworks, MOFs has become of great interest in recent years at the field of multifunctional materials. In this article, we present a study of the effects of size and charge in the anion exchange process of a Gd based MOF, involving molecular species like polyoxometalates (POMs, and [AuCl4]−. This post-synthetic modification has been characterized by IR, EDAX, and single crystal diffraction, which have provided unequivocal evidence of the location of the anion molecules in the framework.

  9. MOF-5 metal-organic framework as sorbent for in-field sampling and preconcentration in combination with thermal desorption GC/MS for determination of atmospheric formaldehyde.

    Science.gov (United States)

    Gu, Zhi-Yuan; Wang, Gen; Yan, Xiu-Ping

    2010-02-15

    Metal-organic frameworks (MOFs) are one kind of highly porous crystalline materials, which are constructed by metal-containing inorganic nodes and organic linkers. With large surface area and high thermal stability, MOFs have great potential as sorbents for the preconcentration of trace analytes. However, such application of MOFs to the analysis of real samples has not been reported before. Here we report the utilization of MOF-5 as sorbent for in-field sampling and preconcentration of atmospheric formaldehyde before thermal desorption (TD) GC/MS (TD-GC/MS) determination without the need for any chemical derivatization. MOF-5 gave a 53 and 73 times better concentration effect than Tenax TA (organic polymers) and Carbograph 1TD (graphitized carbon black), respectively, for TD-GC/MS determination of formaldehyde. MOF-5 showed good performance for in-field sampling and preconcentration of formaldehyde from air samples with a relative humidity less than 45%. The collected formaldehyde on MOF-5 sorbent was stable for at least 72 h at room temperature before TD-GC/MS analysis. One tube packed with 300 mg of MOF-5 lasted 200 cycles of adsorption/TD without significant loss of collection efficiency. The breakthrough volume of such a tube was 1.2 L of 28.35 mg m(-3) formaldehyde at a sampling flow rate of 100 mL min(-1). The use of MOF-5 for in-field sampling and preconcentration in combination with TD-GC/MS for the determination of formaldehyde offered a linear range covering 3 orders of magnitude, and a detection limit of 0.6 microg m(-3). The precision for six replicate cycles of in-field sampling and preconcentration for TD-GC/MS determination using one 300 mg MOF-5 packed tube ranged from 2.8% to 5.3%. The tube-to-tube reproducibility of three MOF-5 tubes prepared in parallel was 7.7%. The developed method was applied to analysis of local indoor and outdoor air samples for formaldehyde and validated by the standard method TO-11A of the United States Environmental

  10. Synthesis and gas adsorption study of porous metal-organic framework materials

    Science.gov (United States)

    Mu, Bin

    Metal-organic frameworks (MOFs) or porous coordination polymers (PCPs) have become the focus of intense study over the past decade due to their potential for advancing a variety of applications including air purification, gas storage, adsorption separations, catalysis, gas sensing, drug delivery, and so on. These materials have some distinct advantages over traditional porous materials such as the well-defined structures, uniform pore sizes, chemically functionalized sorption sites, and potential for postsynthetic modification, etc. Thus, synthesis and adsorption studies of porous MOFs have increased substantially in recent years. Among various prospective applications, air purification is one of the most immediate concerns, which has urgent requirements to improve current nuclear, biological, and chemical (NBC) filters involving commercial and military purposes. Thus, the major goal of this funded project is to search, synthesize, and test these novel hybrid porous materials for adsorptive removal of toxic industrial chemicals (TICs) and chemical warfare agents (CWAs), and to install the benchmark for new-generation NBC filters. The objective of this study is three-fold: (i) Advance our understanding of coordination chemistry by synthesizing novel MOFs and characterizing these porous coordination polymers; (ii) Evaluate porous MOF materials for gasadsorption applications including CO2 capture, CH4 storage, other light gas adsorption and separations, and examine the chemical and physical properties of these solid adsorbents including thermal stability and heat capacity of MOFs; (iii) Evaluate porous MOF materials for next-generation NBC filter media by adsorption breakthrough measurements of TICs on MOFs, and advance our understanding about structureproperty relationships of these novel adsorbents.

  11. Application of MD Simulations to Predict Membrane Properties of MOFs

    Directory of Open Access Journals (Sweden)

    Elda Adatoz

    2015-01-01

    Full Text Available Metal organic frameworks (MOFs are a new group of nanomaterials that have been widely examined for various chemical applications. Gas separation using MOF membranes has become an increasingly important research field in the last years. Several experimental studies have shown that thin-film MOF membranes can outperform well known polymer and zeolite membranes due to their higher gas permeances and selectivities. Given the very large number of available MOF materials, it is impractical to fabricate and test the performance of every single MOF membrane using purely experimental techniques. In this study, we used molecular simulations, Monte Carlo and Molecular Dynamics, to estimate both single-gas and mixture permeances of MOF membranes. Predictions of molecular simulations were compared with the experimental gas permeance data of MOF membranes in order to validate the accuracy of our computational approach. Results show that computational methodology that we described in this work can be used to accurately estimate membrane properties of MOFs prior to extensive experimental efforts.

  12. Probing the structural flexibility of MOFs by constructing metal oxide@MOF-based heterostructures for size-selective photoelectrochemical response

    Science.gov (United States)

    Zhan, Wenwen; He, Yue; Guo, Jiangbin; Chen, Luning; Kong, Xiangjian; Zhao, Haixia; Kuang, Qin; Xie, Zhaoxiong; Zheng, Lansun

    2016-07-01

    It is becoming a challenge to achieve simpler characterization and wider application of flexible metal organic frameworks (MOFs) exhibiting the gate-opening or breathing behavior. Herein, we designed an intelligent MOF-based system where the gate-opening or breathing behavior of MOFs can be facially visualized in solution. Two types of metal oxide@MOF core-shell heterostructures, ZnO@ZIF-7 and ZnO@ZIF-71, were prepared using ZnO nanorods as self-sacrificial templates. The structural flexibility of both the MOFs can be easily judged from the distinct molecular-size-related formation modes and photoelectrochemical performances between the two ZnO@ZIF heterostructures. Moreover, the rotational dynamics of the flexible parts of ZIF-7 were studied by analyzing the intrinsic physical properties, such as dielectric constants, of the structure. The present work reminds us to pay particular attention to the influences of the structural flexibility of MOFs on the structure and properties of MOF-involved heterostructures in future studies.It is becoming a challenge to achieve simpler characterization and wider application of flexible metal organic frameworks (MOFs) exhibiting the gate-opening or breathing behavior. Herein, we designed an intelligent MOF-based system where the gate-opening or breathing behavior of MOFs can be facially visualized in solution. Two types of metal oxide@MOF core-shell heterostructures, ZnO@ZIF-7 and ZnO@ZIF-71, were prepared using ZnO nanorods as self-sacrificial templates. The structural flexibility of both the MOFs can be easily judged from the distinct molecular-size-related formation modes and photoelectrochemical performances between the two ZnO@ZIF heterostructures. Moreover, the rotational dynamics of the flexible parts of ZIF-7 were studied by analyzing the intrinsic physical properties, such as dielectric constants, of the structure. The present work reminds us to pay particular attention to the influences of the structural flexibility of

  13. The quest for modular nanocages: Tbo -MOF as an archetype for mutual substitution, functionalization, and expansion of quadrangular pillar building blocks

    KAUST Repository

    Eubank, Jarrod F.

    2011-09-14

    A new blueprint network for the design and synthesis of porous, functional 3D metal-organic frameworks (MOFs) has been identified, namely, the tbo net. Accordingly, tbo-MOFs based on this unique (3,4)-connected net can be exclusively constructed utilizing a combination of well-known and readily targeted [M(R-BDC)]n MOF layers [i.e., supermolecular building layers (SBLs)] based on the edge-transitive 4,4 square lattice (sql) (i.e., 2D four-building units) and a novel pillaring strategy based on four proximal isophthalate ligands from neighboring SBL membered rings (i.e., two pairs from each layer) covalently cross-linked through an organic quadrangular core (e.g., tetrasubstituted benzene). Our strategy permits the rational design and synthesis of isoreticular structures, functionalized and/or expanded, that possess extra-large nanocapsule-like cages, high porosity, and potential for gas separation and storage, among others. Thus, tbo-MOF serves as an archetypal tunable, isoreticular MOF platform for targeting desired applications. © 2011 American Chemical Society.

  14. Modulations of hMOF autoacetylation by SIRT1 regulate hMOF recruitment and activities on the chromatin

    Institute of Scientific and Technical Information of China (English)

    Lu Lu; Lei Li; Xiang Lv; Xue-Song Wu; De-Pei Liu; Chih-Chuan Liang

    2011-01-01

    A wide variety of nuclear regulators and enzymes are subjected to acetylation of the lysine residue, which regulates different aspects of protein functions. The MYST family histone acetyltransferase, human ortholog of MOF (hMOF), plays critical roles in transcription activation by acetylating nucleosomai H4K16. In this study, we found that hMOF acetylates itself in vitro and in vivo, and the acetylation is restricted to the conserved MYST domain (C2HC zinc finger and HAT), of which the K274 residue is the major autoacetylation site. Furthermore, the class Ⅲ histone deacetylase SIRT1 was found to interact with the MYST domain of hMOF through the deacetylase catalytic region and deacetylate autoacetylated hMOF. In vitro binding assays showed that non-acetylated hMOF robustly binds to nucleosomes while acetylation decreases the binding ability. In HeLa cells, the recruitment of hMOF to the chromatin increases in response to SIRT1 overexpression and decreases after knockdown of SIRT1. The acetylation mimic mutation K274Q apparently decreases the chromatin recruitment of hMOF as well as the global H4K16Ac level in HeLa cells. Finally, upon SIRT1 knockdown, hMOF recruitment to the gene body region of its target gene HoxA9 decreases, accompanied with decrease of H4K16Ac at the same region and repression of HoxA9 transcription. These results suggest a dynamic interplay between SIRT1 and hMOF in regulating H4K16 acetylation.

  15. MOFzyme: Intrinsic protease-like activity of Cu-MOF

    Science.gov (United States)

    Li, Bin; Chen, Daomei; Wang, Jiaqiang; Yan, Zhiying; Jiang, Liang; Deliang Duan; He, Jiao; Luo, Zhongrui; Zhang, Jinping; Yuan, Fagui

    2014-10-01

    The construction of efficient enzyme mimetics for the hydrolysis of peptide bonds in proteins is challenging due to the high stability of peptide bonds and the importance of proteases in biology and industry. Metal-organic frameworks (MOFs) consisting of infinite crystalline lattices with metal clusters and organic linkers may provide opportunities for protease mimic which has remained unknown. Herein, we report that Cu2(C9H3O6)4/3 MOF (which is well known as HKUST-1 and denoted as Cu-MOF here), possesses an intrinsic enzyme mimicking activity similar to that found in natural trypsin to bovine serum albumin (BSA) and casein. The Michaelis constant (Km) of Cu-MOF is about 26,000-fold smaller than that of free trypsin indicating a much higher affinity of BSA for Cu-MOF surface. Cu-MOF also exhibited significantly higher catalytic efficiency than homogeneous artificial metalloprotease Cu(II) complexes and could be reused for ten times without losing in its activity. Moreover, Cu-MOF was successfully used to simulate trypsinization in cell culture since it dissociated cells in culture even without EDTA.

  16. The Functional Analysis of Histone Acetyltransferase MOF in Tumorigenesis

    Directory of Open Access Journals (Sweden)

    Jiaming Su

    2016-01-01

    Full Text Available Changes in chromatin structure and heritably regulating the gene expression by epigenetic mechanisms, such as histone post-translational modification, are involved in most cellular biological processes. Thus, abnormal regulation of epigenetics is implicated in the occurrence of various diseases, including cancer. Human MOF (males absent on the first is a member of the MYST (Moz-Ybf2/Sas3-Sas2-Tip60 family of histone acetyltransferases (HATs. As a catalytic subunit, MOF can form at least two distinct multiprotein complexes (MSL and NSL in human cells. Both complexes can acetylate histone H4 at lysine 16 (H4K16; however, the NSL complex possesses broader substrate specificity and can also acetylate histone H4 at lysines 5 and 8 (H4K5 and H4K8, suggesting the complexity of the intracellular functions of MOF. Silencing of MOF in cells leads to genomic instability, inactivation of gene transcription, defective DNA damage repair and early embryonic lethality. Unbalanced MOF expression and its corresponding acetylation of H4K16 have been found in certain primary cancer tissues, including breast cancer, medulloblastoma, ovarian cancer, renal cell carcinoma, colorectal carcinoma, gastric cancer, as well as non-small cell lung cancer. In this review, we provide a brief overview of MOF and its corresponding histone acetylation, introduce recent research findings that link MOF functions to tumorigenesis and speculate on the potential role that may be relevant to tumorigenic pathways.

  17. Gas sensing using porous materials for automotive applications.

    Science.gov (United States)

    Wales, Dominic J; Grand, Julien; Ting, Valeska P; Burke, Richard D; Edler, Karen J; Bowen, Chris R; Mintova, Svetlana; Burrows, Andrew D

    2015-07-01

    Improvements in the efficiency of combustion within a vehicle can lead to reductions in the emission of harmful pollutants and increased fuel efficiency. Gas sensors have a role to play in this process, since they can provide real time feedback to vehicular fuel and emissions management systems as well as reducing the discrepancy between emissions observed in factory tests and 'real world' scenarios. In this review we survey the current state-of-the-art in using porous materials for sensing the gases relevant to automotive emissions. Two broad classes of porous material - zeolites and metal-organic frameworks (MOFs) - are introduced, and their potential for gas sensing is discussed. The adsorptive, spectroscopic and electronic techniques for sensing gases using porous materials are summarised. Examples of the use of zeolites and MOFs in the sensing of water vapour, oxygen, NOx, carbon monoxide and carbon dioxide, hydrocarbons and volatile organic compounds, ammonia, hydrogen sulfide, sulfur dioxide and hydrogen are then detailed. Both types of porous material (zeolites and MOFs) reveal great promise for the fabrication of sensors for exhaust gases and vapours due to high selectivity and sensitivity. The size and shape selectivity of the zeolite and MOF materials are controlled by variation of pore dimensions, chemical composition (hydrophilicity/hydrophobicity), crystal size and orientation, thus enabling detection and differentiation between different gases and vapours. PMID:25982991

  18. Positronium in MOFs: the Atom out of the box

    CERN Document Server

    Crivelli, P; Barbiellini, B; Brown, B L; Feldblyum, J I; Guo, P; Gidley, D W; Gerchow, L; Matzger, A J

    2013-01-01

    Recently, evidence for positronium (Ps) in a Bloch state in self-assembled metal--organic frameworks (MOFs) has been reported [Dutta et al., Phys. Rev. Lett. 110, 197403 (2013)]. In this paper, we study Ps emission into vacuum from four different MOFs crystals: MOF-5, IRMOF-8, FMA and IRMOF-20. Our measurements of Ps yield and emission energy into vacuum provide definitive evidence of Ps delocalization. We determine with a different technique Ps diffusion lengths in agreement with the recently published results. Furthermore, we measure that a fraction of the Ps is emitted into vacuum with a distinctly smaller energy than what one would expect for Ps localized in the MOFs' cells. We show that a calculation assuming Ps delocalized in a Kronig--Penney potential reproduces the measured Ps emission energy.

  19. Finely tuning MOFs towards high-performance post-combustion CO2 capture materials.

    Science.gov (United States)

    Wang, Qian; Bai, Junfeng; Lu, Zhiyong; Pan, Yi; You, Xiaozeng

    2016-01-11

    CO2 capture science and technology, particularly for the post-combustion CO2 capture, has become one of very important research fields, due to great concern of global warming. Metal-organic frameworks (MOFs) with a unique feature of structural fine-tunability, unlike the traditional porous solid materials, can provide many and powerful platforms to explore high-performance adsorbents for post-combustion CO2 capture. Until now, several strategies for finely tuning MOF structures have been developed, in which either the larger quadrupole moment and polarizability of CO2 are considered: metal ion change (I), functional groups attachment (II) and functional group insertion (III), vary the electronic nature of the pore surface; or targeting the smaller kinetic diameter of CO2 over N2 is focused on: framework interpenetration (IV), ligand shortening (V) and coordination site shifting (VI) contract the pore size of frameworks to improve their CO2 capture properties. In this review, from the viewpoint of synthetic materials scientists/chemists, we would like to introduce and summarize these strategies based upon recent work published by other groups and ourselves. PMID:26512792

  20. Design and synthesis of squaramide-based MOFs as efficient MOF-supported hydrogen-bonding organocatalysts.

    Science.gov (United States)

    Zhang, Xiaoping; Zhang, Zhenjie; Boissonnault, Jake; Cohen, Seth M

    2016-06-30

    Herein, we utilize a new, squaramide-based ligand, combined with a postsynthetic exchange (PSE) synthetic approach to prepare a series of Cu(ii)-squaramide MOFs that are active catalysts for the Friedel-Crafts reaction. PMID:27320848

  1. Structure and Mobility of Metal Clusters in MOFs: Au, Pd, and AuPd Clusters in MOF-74

    DEFF Research Database (Denmark)

    Vilhelmsen, Lasse; Walton, Krista S.; Sholl, David S.

    2012-01-01

    Understanding the adsorption and mobility of metal–organic framework (MOF)-supported metal nanoclusters is critical to the development of these catalytic materials. We present the first theoretical investigation of Au-, Pd-, and AuPd-supported clusters in a MOF, namely MOF-74. We combine density...... functional theory (DFT) calculations with a genetic algorithm (GA) to reliably predict the structure of the adsorbed clusters. This approach allows comparison of hundreds of adsorbed configurations for each cluster. From the investigation of Au8, Pd8, and Au4Pd4 we find that the organic part of the MOF...... is just as important for nanocluster adsorption as open Zn or Mg metal sites. Using the large number of clusters generated by the GA, we developed a systematic method for predicting the mobility of adsorbed clusters. Through the investigation of diffusion paths a relationship between the cluster...

  2. Synthesis of Framework Isomer MOFs Containing Zinc and 4-Tetrazolyl Benzenecarboxylic Acid via a Structure Directing Solvothermal Approach

    Directory of Open Access Journals (Sweden)

    Carlos Ordonez

    2015-04-01

    Full Text Available The solvothermal synthesis of framework isomers was carried out using the hybrid carboxylate and tetrazolate functional ligand, 4-tetrazolyl benzenecarboxylic acid (H2TBC, TBC = 4-tetrazolyl benzenecarboxylate and zinc. H2TBC was also synthesized with the solvothermal approach, and is referred herein as structure 1. Using single-crystal X-ray diffraction, we found that the tetrazolate groups of TBC show an unusual “opposite-on” coordination mode with zinc. Three previously characterized metal-organic frameworks (MOFs were obtained by systematically changing the solvents of the H2TBC-Zn reaction, (1 ZnTBC, 2, which has a non-porous structure; (2 Zn2(TBC2(H2O, 3, which has an amphiphilic pore structure and (3 Zn2(TBC2{guest}, 4, which is porous and has channels containing uncoordinated N heteroatoms. Fluorescence spectra of 4 reveal a strong blue emission mainly from the TBC ligands.

  3. A novel 3D energetic MOF of high energy content: synthesis and superior explosive performance of a Pb(ii) compound with 5,5'-bistetrazole-1,1'-diolate.

    Science.gov (United States)

    Shang, Yu; Jin, Bo; Peng, Rufang; Liu, Qiangqiang; Tan, Bisheng; Guo, Zhicheng; Zhao, Jun; Zhang, Qingchun

    2016-09-21

    The development of high-performance insensitive energetic materials is important because of the increasing demand for these materials in military and civilian applications. A novel 3D energetic metal-organic framework (MOF) of exceptionally high energy content, [Pb(BTO)(H2O)]n, was synthesized and structurally characterized by single crystal X-ray diffraction, featuring a three-dimensional parallelogram porous framework, where BTO represents 5,5'-bistetrazole-1,1'-diolate. The thermal stability and energetic properties were determined, exhibiting good thermostability (Td = 309.0 °C), excellent detonation pressure (P) of 53.06 GPa, a detonation velocity (D) of 9.204 km s(-1), and acceptable sensitivity to confirmed impact (IS = 7.5 J). Notably, the complex possesses unprecedented superior density than the reported energetic MOFs. The results highlight this new MOF as a potential energetic material. PMID:27518537

  4. A novel 3D energetic MOF of high energy content: synthesis and superior explosive performance of a Pb(ii) compound with 5,5'-bistetrazole-1,1'-diolate.

    Science.gov (United States)

    Shang, Yu; Jin, Bo; Peng, Rufang; Liu, Qiangqiang; Tan, Bisheng; Guo, Zhicheng; Zhao, Jun; Zhang, Qingchun

    2016-09-21

    The development of high-performance insensitive energetic materials is important because of the increasing demand for these materials in military and civilian applications. A novel 3D energetic metal-organic framework (MOF) of exceptionally high energy content, [Pb(BTO)(H2O)]n, was synthesized and structurally characterized by single crystal X-ray diffraction, featuring a three-dimensional parallelogram porous framework, where BTO represents 5,5'-bistetrazole-1,1'-diolate. The thermal stability and energetic properties were determined, exhibiting good thermostability (Td = 309.0 °C), excellent detonation pressure (P) of 53.06 GPa, a detonation velocity (D) of 9.204 km s(-1), and acceptable sensitivity to confirmed impact (IS = 7.5 J). Notably, the complex possesses unprecedented superior density than the reported energetic MOFs. The results highlight this new MOF as a potential energetic material.

  5. File list: Oth.ALL.10.mof.AllCell [Chip-atlas[Archive

    Lifescience Database Archive (English)

    Full Text Available Oth.ALL.10.mof.AllCell dm3 TFs and others mof All cell types SRX287892,SRX146999,ER...X101806,ERX101804,SRX287891,SRX146998 http://dbarchive.biosciencedbc.jp/kyushu-u/dm3/assembled/Oth.ALL.10.mof.AllCell.bed ...

  6. File list: Oth.ALL.50.mof.AllCell [Chip-atlas[Archive

    Lifescience Database Archive (English)

    Full Text Available Oth.ALL.50.mof.AllCell dm3 TFs and others mof All cell types SRX146999,ERX101806,ER...X101804,SRX287892,SRX146998,SRX287891 http://dbarchive.biosciencedbc.jp/kyushu-u/dm3/assembled/Oth.ALL.50.mof.AllCell.bed ...

  7. Loading of Two Related Metal-Organic Frameworks (MOFs, [Cu2(bdc2(dabco] and [Cu2(ndc2(dabco], with Ferrocene

    Directory of Open Access Journals (Sweden)

    Wolfgang Wenzel

    2011-09-01

    Full Text Available We have studied the loading of two related, similar porous metal-organic frameworks (MOFs [Cu2(bdc2(dabco] (1, and [Cu2(ndc2(dabco] (2 with ferrocene by exposing bulk powder samples to the corresponding vapor. On the basis of powder X-ray diffraction data and molecular dynamics (MD calculations we propose that each pore can store one ferrocene molecule. Despite the rather pronounced similarity of the two MOFs a quite different behavior is observed, for 1 loading with ferrocene leads to an anisotropic 1% contraction, whereas for 2 no deformation is observed. Mössbauer spectroscopy studies reveal that the Fe oxidation level remains unchanged during the process. Time dependent studies reveal that the diffusion constant governing the loading from the gas-phase for 1 is approximately three times larger than the value for 2.

  8. 2-periodic metal-organic frameworks (MOFs) as supermolecular building layers (SBLs) for making targeted 3-periodic MOFs

    KAUST Repository

    Eddaoudi, Mohamed

    2015-09-22

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

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

    NARCIS (Netherlands)

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

    2013-01-01

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

  10. Expanded organic building units for the construction of highly porous metal-organic frameworks.

    Science.gov (United States)

    Kong, Guo-Qiang; Han, Zhi-Da; He, Yabing; Ou, Sha; Zhou, Wei; Yildirim, Taner; Krishna, Rajamani; Zou, Chao; Chen, Banglin; Wu, Chuan-De

    2013-10-25

    Two new organic building units that contain dicarboxylate sites for their self-assembly with paddlewheel [Cu2(CO2)4] units have been successfully developed to construct two isoreticular porous metal-organic frameworks (MOFs), ZJU-35 and ZJU-36, which have the same tbo topologies (Reticular Chemistry Structure Resource (RCSR) symbol) as HKUST-1. Because the organic linkers in ZJU-35 and ZJU-36 are systematically enlarged, the pores in these two new porous MOFs vary from 10.8 Å in HKUST-1 to 14.4 Å in ZJU-35 and 16.5 Å in ZJU-36, thus leading to their higher porosities with Brunauer-Emmett-Teller (BET) surface areas of 2899 and 4014 m(2) g(-1) for ZJU-35 and ZJU-36, respectively. High-pressure gas-sorption isotherms indicate that both ZJU-35 and ZJU-36 can take up large amounts of CH4 and CO2, and are among the few porous MOFs with the highest volumetric storage of CH4 under 60 bar and CO2 under 30 bar at room temperature. Their potential for high-pressure swing adsorption (PSA) hydrogen purification was also preliminarily examined and compared with several reported MOFs, thus indicating the potential of ZJU-35 and ZJU-36 for this important application. Studies show that most of the highly porous MOFs that can volumetrically take up the greatest amount of CH4 under 60 bar and CO2 under 30 bar at room temperature are those self-assembled from organic tetra- and hexacarboxylates that contain m-benzenedicarboxylate units with the [Cu2(CO2)4] units, because this series of MOFs can have balanced porosities, suitable pores, and framework densities to optimize their volumetric gas storage. The realization of the two new organic building units for their construction of highly porous MOFs through their self-assembly with [Cu2(CO2)4] units has provided great promise for the exploration of a large number of new tetra- and hexacarboxylate organic linkers based on these new organic building units in which different aromatic backbones can be readily incorporated

  11. MOF compounds for the cry-adsorption of hydrogen. Improvement of the heat transfer and volumetric storage density; MOF-Materialien zur Kryoadsorption von Wasserstoff. Verbesserung von Waermetransfer und volumetrischer Speicherdichte

    Energy Technology Data Exchange (ETDEWEB)

    Jahn, Alexander [Technische Univ. Dresden (Germany). Inst. fuer Energietechnik; Fraunhofer-Institut fuer Fertigungstechnik und Angewandte Materialforschung IFAM, Dresden (Germany); Klaus, Marcel; Haberstroh, Christoph [Technische Univ. Dresden (Germany). Inst. fuer Energietechnik; Roentzsch, Lars [Fraunhofer-Institut fuer Fertigungstechnik und Angewandte Materialforschung IFAM, Dresden (Germany)

    2012-07-01

    The authors of the contribution under consideration report on new composite materials consisting of metal-organic framework compounds (MOF) and graphite for the cry-adsorption of hydrogen (H{sub 2}) at a temperature of 77 K. These composite materials are characterized by an enhanced volumetric and gravimetric storage density for H{sub 2}. Mixtures consisting of Cu-BTC (BTC = benzene-1.3.5-tricarboxylate) as a highly porous metal-organic framework compound and a highly thermally conductive natural graphite were mixed to a compact composite material by a powder-technological process route. Cylindrical pellets of this composite material were implemented in a tube reactor. This tube reactor was integrated in a specially developed test rig environment and used for experiments for adsorption and desorption of hydrogen. The main focus is thereby on the temperature progression within the reaction bed in order to draw conclusions on the extent and dynamics of the heating of the storage material due to the exothermal adsorption of hydrogen. As it could be shown, the enhancement of the effective thermal conductivity of the storage material due to the incorporate graphite affects the storage rate of the composite material. This is a significant advantage in comparison to bulk powder of MOF. In addition to the direct results, the authors also report on the test rig as well as application examples.

  12. Two porous luminescent metal-organic frameworks: quantifiable evaluation of dynamic and static luminescent sensing mechanisms towards Fe(3.).

    Science.gov (United States)

    Jin, Jun-Cheng; Pang, Ling-Yan; Yang, Guo-Ping; Hou, Lei; Wang, Yao-Yu

    2015-10-21

    Two novel porous luminescent metal-organic frameworks (MOFs, 1 and 2) have been constructed using 3,4-di(3,5-dicarboxyphenyl)phthalic acid using a hydrothermal method. Both MOFs can work as highly sensitive sensors to Fe(3+) by luminescent quenching. Analyses of the structures indicate a higher quenching efficiency of 2 because of the existence of active -COOH groups. Based on this consideration, the quenching mechanisms are studied and the processes are controlled by multiple mechanisms in which dynamic and static mechanisms of MOFs are discussed. Besides, the corresponding dynamic and static quenching constants are calculated, achieving the quantification evaluation of the quenching process. As expected, experimental data show that compound 2 possesses an overall quenching efficiency 6.9 times that of compound 1. Additionally, time-dependent intensity measurements, the shifts of the excitation spectrum and the appearance of a new emission peak all give visual proofs of the distinct mechanisms between the two MOFs.

  13. MOFs for storage of natural gas in mobile applications

    Energy Technology Data Exchange (ETDEWEB)

    Marx, S.; Arnold, L.; Gaab, M.; Maurer, S.; Weickert, M.; Mueller, U. [BASF SE, Ludwigshafen (Germany); Gummaraju, R.; SantaMaria, M.; Wilson, K.; Garbotz, C.; Lynch, J. [BASF Corporation, Iselin, NJ (United States)

    2013-11-01

    Metal-organic frameworks (MOFs) are supposed to have high potential in gas storage, particular in the storage of natural gas (NG) for mobile applications. Due to the shale gas exploration and the cost advantage of natural gas on the North American market as well as the environmental benign behavior upon combustion, storage of gaseous fuels will become more important for future mobility. The main challenge with all gaseous fuels is the limited range of the fuel stored on board of a vehicle. Instead of increasing the pressure in the tank, which would lead to heavy tanks and high compression costs, MOFs might help to improve the energy density of the gas stored in a tank resulting in an increased driving distance or reduced space needed for the gas tanks. (orig.)

  14. Application of MD Simulations to Predict Membrane Properties of MOFs

    OpenAIRE

    Elda Adatoz; Seda Keskin

    2015-01-01

    Research Article Application of MD Simulations to Predict Membrane Properties of MOFs Elda Adatoz and Seda Keskin Chemical and Biological Engineering, Koc University, Rumelifeneri Yolu, Sariyer, 34450 Istanbul, Turkey Correspondence should be addressed to Seda Keskin; Received 22 May 2015; Accepted 13 July 2015 Academic Editor: Yanlin Song Copyright © 2015 E. Adatoz and S. Keskin. This is an open access article distributed under the Creative Commons A...

  15. Insights on Capacitive Interdigitated Electrodes Coated with MOF Thin Films: Humidity and VOCs Sensing as a Case Study.

    Science.gov (United States)

    Sapsanis, Christos; Omran, Hesham; Chernikova, Valeriya; Shekhah, Osama; Belmabkhout, Youssef; Buttner, Ulrich; Eddaoudi, Mohamed; Salama, Khaled N

    2015-01-01

    A prototypical metal-organic framework (MOF), a 2D periodic porous structure based on the assembly of copper ions and benzene dicarboxylate (bdc) ligands (Cu(bdc)·xH2O), was grown successfully as a thin film on interdigitated electrodes (IDEs). IDEs have been used for achieving planar CMOS-compatible low-cost capacitive sensing structures for the detection of humidity and volatile organic compounds (VOCs). Accordingly, the resultant IDEs coated with the Cu(bdc)·xH2O thin film was evaluated, for the first time, as a capacitive sensor for gas sensing applications. A fully automated setup, using LabVIEW interfaces to experiment conduction and data acquisition, was developed in order to measure the associated gas sensing performance. PMID:26213943

  16. Insights on Capacitive Interdigitated Electrodes Coated with MOF Thin Films: Humidity and VOCs Sensing as a Case Study

    KAUST Repository

    Sapsanis, Christos

    2015-07-24

    A prototypical metal-organic framework (MOF), a 2D periodic porous structure based on the assembly of copper ions and benzene dicarboxylate (bdc) ligands (Cu(bdc)·xH2O), was grown successfully as a thin film on interdigitated electrodes (IDEs). IDEs have been used for achieving planar CMOS-compatible low-cost capacitive sensing structures for the detection of humidity and volatile organic compounds (VOCs). Accordingly, the resultant IDEs coated with the Cu(bdc)·xH2O thin film was evaluated, for the first time, as a capacitive sensor for gas sensing applications. A fully automated setup, using LabVIEW interfaces to experiment conduction and data acquisition, was developed in order to measure the associated gas sensing performance.

  17. Insights on Capacitive Interdigitated Electrodes Coated with MOF Thin Films: Humidity and VOCs Sensing as a Case Study

    Directory of Open Access Journals (Sweden)

    Christos Sapsanis

    2015-07-01

    Full Text Available A prototypical metal-organic framework (MOF, a 2D periodic porous structure based on the assembly of copper ions and benzene dicarboxylate (bdc ligands (Cu(bdc·xH2O, was grown successfully as a thin film on interdigitated electrodes (IDEs. IDEs have been used for achieving planar CMOS-compatible low-cost capacitive sensing structures for the detection of humidity and volatile organic compounds (VOCs. Accordingly, the resultant IDEs coated with the Cu(bdc·xH2O thin film was evaluated, for the first time, as a capacitive sensor for gas sensing applications. A fully automated setup, using LabVIEW interfaces to experiment conduction and data acquisition, was developed in order to measure the associated gas sensing performance.

  18. Regulation of the histone acetyltransferase activity of hMOF via autoacetylation of Lys274

    Institute of Scientific and Technical Information of China (English)

    Bingfa Sun; Shunling Guo; Qingyu Tang; Chen Li; Rong Zeng; Zhiqi Xiong; Chen Zhong; Jianping Ding

    2011-01-01

    Dear Editor, Males-absent-on-the-first (MOF, also called MYST1 or KAT8) is a histone acetyltransferase (HAT) belonging to the MOZ, Ybf2/Sas3, Sas2 and Tip60 (MYST) family.MOF has been shown to possess a specific HAT activity towards Lysl6 of histone H4 (H4K16) [1].Homozygous knockout of MOF in mice results in loss of H4K16 acetylation and embryonic lethality, indicating that MOF and H4K16 acetylation are essential for embryogenesis and genome stability in mammals [2].Downregulation of human MOF (hMOF) leads to dramatic nuclear morphological deformation and inhibition of cell cycle progression [3], and has recently been correlated with primary breast carcinoma and medulloblastoma [4].

  19. Catalytically Active Bimetallic Nanoparticles Supported on Porous Carbon Capsules Derived From Metal-Organic Framework Composites.

    Science.gov (United States)

    Yang, Hui; Bradley, Siobhan J; Chan, Andrew; Waterhouse, Geoffrey I N; Nann, Thomas; Kruger, Paul E; Telfer, Shane G

    2016-09-14

    We report a new methodology for producing monometallic or bimetallic nanoparticles confined within hollow nitrogen-doped porous carbon capsules. The capsules are derived from metal-organic framework (MOF) crystals that are coated with a shell of a secondary material comprising either a metal-tannic acid coordination polymer or a resorcinol-formaldehyde polymer. Platinum nanoparticles are optionally sandwiched between the MOF core and the shell. Pyrolysis of the MOF-shell composites produces hollow capsules of porous nitrogen-doped carbon that bear either monometallic (Pt, Co, and Ni) or alloyed (PtCo and PtNi) metal nanoparticles. The Co and Ni components of the bimetallic nanoparticles are derived from the shell surrounding the MOF crystals. The hollow capsules prevent sintering and detachment of the nanoparticles, and their porous walls allow for efficient mass transport. Alloyed PtCo nanoparticles embedded in the capsule walls are highly active, selective, and recyclable catalysts for the hydrogenation of nitroarenes to anilines. PMID:27575666

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

    Science.gov (United States)

    Ma, Shengqian; Zhou, Hong-Cai

    2010-01-01

    Depletion of fossil oil deposits and the escalating threat of global warming have put clean energy research, which includes the search for clean energy carriers such as hydrogen and methane as well as the reduction of carbon dioxide emissions, on the urgent agenda. A significant technical challenge has been recognized as the development of a viable method to efficiently trap hydrogen, methane and carbon dioxide gas molecules in a confined space for various applications. This issue can be addressed by employing highly porous materials as storage media, and porous metal-organic frameworks (MOFs) which have exceptionally high surface areas as well as chemically-tunable structures are playing an unusual role in this respect. In this feature article we provide an overview of the current status of clean energy applications of porous MOFs, including hydrogen storage, methane storage and carbon dioxide capture. PMID:20024292

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

    Science.gov (United States)

    Ma, Shengqian; Zhou, Hong-Cai

    2010-01-01

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

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

    Science.gov (United States)

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

    2013-04-01

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

  3. Postsynthetic modification of an amino-tagged MOF using peptide coupling reagents: a comparative study.

    Science.gov (United States)

    Hintz, Henrik; Wuttke, Stefan

    2014-10-01

    The suitability of four peptide coupling reagents for postsynthetic modification (PSM) of amino-tagged metal-organic frameworks (MOFs) with carboxylic acids was investigated. Mild reaction conditions at room temperature allow effective covalent attachment of drugs and biomolecules inside the pores of MOFs with moderate chemical stability.

  4. Computational Screening of MOF-Based Mixed Matrix Membranes for CO2/N2 Separations

    Directory of Open Access Journals (Sweden)

    Zeynep Sumer

    2016-01-01

    Full Text Available Atomically detailed simulations were used to examine CO2/N2 separation potential of metal organic framework- (MOF- based mixed matrix membranes (MMMs in this study. Gas permeability and selectivity of 700 new MMMs composed of 70 different MOFs and 10 different polymers were calculated for CO2/N2 separation. This is the largest number of MOF-based MMMs for which computational screening is done to date. Selecting the appropriate MOFs as filler particles in polymers resulted in MMMs that have higher CO2/N2 selectivities and higher CO2 permeabilities compared to pure polymer membranes. We showed that, for polymers that have low CO2 permeabilities but high CO2 selectivities, the identity of the MOF used as filler is not important. All MOFs enhanced the CO2 permeabilities of this type of polymers without changing their selectivities. Several MOF-based MMMs were identified to exceed the upper bound established for polymers. The methods we introduced in this study will create many opportunities to select the MOF/polymer combinations with useful properties for CO2 separation applications.

  5. Direct observations of the MOF (UiO-66) structure by transmission electron microscopy

    KAUST Repository

    Zhu, Liangkui

    2013-01-01

    As a demonstration of ab initio structure characterizations of nano metal organic framework (MOF) crystals by high resolution transmission electron microscopy (HRTEM) and electron diffraction tomography methods, a Zr-MOF (UiO-66) structure was determined and further confirmed by Rietveld refinements of powder X-ray diffraction. HRTEM gave direct imaging of the channels. © 2013 The Royal Society of Chemistry.

  6. Mixed matrix membranes with strengthened MOFs/polymer interfacial interaction and improved membrane performance.

    Science.gov (United States)

    Lin, Rijia; Ge, Lei; Hou, Lei; Strounina, Ekaterina; Rudolph, Victor; Zhu, Zhonghua

    2014-04-23

    MOFs-based mixed matrix membranes (MMMs) have attracted extensive attention in recent years due to their potential high separation performance, the low cost, and good mechanical properties. However, it is still very challenging to achieve defect-free interface between micrometer-sized MOFs and a polymer matrix. In this study, [Cd2L(H2O)]2·5H2O (Cd-6F) synthesized using 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) as an organic ligand was introduced into the 6FDA-ODA polyimide matrix to achieve novel MOF MMMs. A specific interfacial interaction between MOF crystals and polymer chains was innovatively targeted and achieved through in situ polymerization procedure. The enhanced adhesion between MOF particles and polymer phase was observed, and the improved interfacial interaction between Cd-6F and the 6FDA-ODA polyimide matrix was confirmed by detailed characterizations including FTIR and NMR. In the meantime, the gas permeance and selectivity of the MMMs are strongly dependent on their morphology. The MMM derived from in situ polymerization presents excellent interfaces between micrometer-sized MOF crystals and the polymer matrix, resulting in increased permeability and selectivity. The strategy shown here can be further utilized to select the MOF/polymer pair, eliminate interfacial voids, and improve membrane separation performance of MOFs-based MMMs.

  7. Facile "modular assembly" for fast construction of a highly oriented crystalline MOF nanofilm.

    Science.gov (United States)

    Xu, Gang; Yamada, Teppei; Otsubo, Kazuya; Sakaida, Shun; Kitagawa, Hiroshi

    2012-10-10

    The preparation of crystalline, ordered thin films of metal-organic frameworks (MOFs) will be a critical process for MOF-based nanodevices in the future. MOF thin films with perfect orientation and excellent crystallinity were formed with novel nanosheet-structured components, Cu-TCPP [TCPP = 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin], by a new "modular assembly" strategy. The modular assembly process involves two steps: a "modularization" step is used to synthesize highly crystalline "modules" with a nanosized structure that can be conveniently assembled into a thin film in the following "assembly" step. With this method, MOF thin films can easily be set up on different substrates at very high speed with controllable thickness. This new approach also enabled us to prepare highly oriented crystalline thin films of MOFs that cannot be prepared in thin-film form by traditional techniques.

  8. Mg-MOF-74@SBA-15 hybrids: Synthesis, characterization, and adsorption properties

    Energy Technology Data Exchange (ETDEWEB)

    Chakraborty, Anindita; Maji, Tapas Kumar, E-mail: tmaji@jncasr.ac.in [Molecular Materials Laboratory, Chemistry and Physics of Materials Unit, Jawaharlal Nehru Centre for Advanced Scientific Research, Jakkur, Bangalore 560064 (India)

    2014-12-01

    Nanocrystals of Mg-MOF-74 have been immobilized into the mesopores of SBA-15 rods to fabricate Mg-MOF-74@SBA-15 hybrid materials. To furnish such composites, a relatively simple synthetic strategy has been adopted by direct dispersion of the metal-organic framework (MOF) precursors in SBA-15 matrix to prepare the hybrid materials in situ. The hybrid materials have been characterized using powder X-ray diffraction and several spectroscopic and microscopic techniques, which suggest growth of the MOF nanocrystals inside the SBA-15 mesopores and the composites exhibit characteristics of both the components. N{sub 2} adsorption isotherms at 77 K reveal that the composites contain additional mesopores, compared to only micropores of pristine MOF nanocrystals. In addition to such combination of both micro and mesoporosity, the composites also demonstrate significant CO{sub 2} adsorption at room temperature.

  9. Forming MOFs into spheres by use of molecular gastronomy methods.

    Science.gov (United States)

    Spjelkavik, Aud I; Aarti; Divekar, Swapnil; Didriksen, Terje; Blom, Richard

    2014-07-14

    A novel method utilizing hydrocolloids to prepare nicely shaped spheres of metal-organic frameworks (MOFs) has been developed. Microcrystalline CPO-27-Ni particles are dispersed in either alginate or chitosan solutions, which are added dropwise to solutions containing, respectively, either divalent group 2 cations or base that act as gelling agents. Well-shaped spheres are immediately formed, which can be dried into spheres containing mainly MOF (>95 wt %). The spheronizing procedures have been optimized with respect to maximum specific surface area, shape, and particle density of the final sphere. At optimal conditions, well-shaped 2.5-3.5 mm diameter CPO-27-Ni spheres with weight-specific surface areas <10 % lower than the nonformulated CPO-27-Ni precursor, and having sphere densities in the range 0.8 to 0.9 g cm(-3) and particle crushing strengths above 20 N, can be obtained. The spheres are well suited for use in fixed-bed catalytic or adsorption processes.

  10. Forming MOFs into spheres by use of molecular gastronomy methods.

    Science.gov (United States)

    Spjelkavik, Aud I; Aarti; Divekar, Swapnil; Didriksen, Terje; Blom, Richard

    2014-07-14

    A novel method utilizing hydrocolloids to prepare nicely shaped spheres of metal-organic frameworks (MOFs) has been developed. Microcrystalline CPO-27-Ni particles are dispersed in either alginate or chitosan solutions, which are added dropwise to solutions containing, respectively, either divalent group 2 cations or base that act as gelling agents. Well-shaped spheres are immediately formed, which can be dried into spheres containing mainly MOF (>95 wt %). The spheronizing procedures have been optimized with respect to maximum specific surface area, shape, and particle density of the final sphere. At optimal conditions, well-shaped 2.5-3.5 mm diameter CPO-27-Ni spheres with weight-specific surface areas <10 % lower than the nonformulated CPO-27-Ni precursor, and having sphere densities in the range 0.8 to 0.9 g cm(-3) and particle crushing strengths above 20 N, can be obtained. The spheres are well suited for use in fixed-bed catalytic or adsorption processes. PMID:24964774

  11. MOFs under pressure: the reversible compression of a single crystal.

    Science.gov (United States)

    Gagnon, Kevin J; Beavers, Christine M; Clearfield, Abraham

    2013-01-30

    The structural change and resilience of a single crystal of a metal-organic framework (MOF), Zn(HO(3)PC(4)H(8)PO(3)H)·2H(2)O (ZAG-4), was investigated under high pressures (0-9.9 GPa) using in situ single crystal X-ray diffraction. Although the unit cell volume decreases over 27%, the quality of the single crystal is retained and the unit cell parameters revert to their original values after pressure has been removed. This framework is considerably compressible with a bulk modulus calculated at ∼11.7 GPa. The b-axis also exhibits both positive and negative linear compressibility. Within the applied pressures investigated, there was no discernible failure or amorphization point for this compound. The alkyl chains in the structure provide a spring-like cushion to stabilize the compression of the system allowing for large distortions in the metal coordination environment, without destruction of the material. This intriguing observation only adds to the current speculation as to whether or not MOFs may find a role as a new class of piezofunctional solid-state materials for application as highly sensitive pressure sensors, shock absorbing materials, pressure switches, or smart body armor. PMID:23320490

  12. Robust, chiral, and porous BINAP-based metal-organic frameworks for highly enantioselective cyclization reactions.

    Science.gov (United States)

    Sawano, Takahiro; Thacker, Nathan C; Lin, Zekai; McIsaac, Alexandra R; Lin, Wenbin

    2015-09-30

    We report here the design of BINAP-based metal-organic frameworks and their postsynthetic metalation with Rh complexes to afford highly active and enantioselective single-site solid catalysts for the asymmetric cyclization reactions of 1,6-enynes. Robust, chiral, and porous Zr-MOFs of UiO topology, BINAP-MOF (I) or BINAP-dMOF (II), were prepared using purely BINAP-derived dicarboxylate linkers or by mixing BINAP-derived linkers with unfunctionalized dicarboxylate linkers, respectively. Upon metalation with Rh(nbd)2BF4 and [Rh(nbd)Cl]2/AgSbF6, the MOF precatalysts I·Rh(BF4) and I·Rh(SbF6) efficiently catalyzed highly enantioselective (up to 99% ee) reductive cyclization and Alder-ene cycloisomerization of 1,6-enynes, respectively. I·Rh catalysts afforded cyclization products at comparable enantiomeric excesses (ee's) and 4-7 times higher catalytic activity than the homogeneous controls, likely a result of catalytic site isolation in the MOF which prevents bimolecular catalyst deactivation pathways. However, I·Rh is inactive in the more sterically encumbered Pauson-Khand reactions between 1,6-enynes and carbon monoxide. In contrast, with a more open structure, Rh-functionalized BINAP-dMOF, II·Rh, effectively catalyzed Pauson-Khand cyclization reactions between 1,6-enynes and carbon monoxide at 10 times higher activity than the homogeneous control. II·Rh was readily recovered and used three times in Pauson-Khand cyclization reactions without deterioration of yields or ee's. Our work has expanded the scope of MOF-catalyzed asymmetric reactions and showed that the mixed linker strategy can effectively enlarge the open space around the catalytic active site to accommodate highly sterically demanding polycyclic metallocycle transition states/intermediates in asymmetric intramolecular cyclization reactions. PMID:26335305

  13. Robust, Chiral, and Porous BINAP-Based Metal–Organic Frameworks for Highly Enantioselective Cyclization Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Sawano, Takahiro; Thacker, Nathan C.; Lin, Zekai; McIsaac, Alexandra R.; Lin, Wenbin (UC)

    2016-05-06

    We report here the design of BINAP-based metal–organic frameworks and their postsynthetic metalation with Rh complexes to afford highly active and enantioselective single-site solid catalysts for the asymmetric cyclization reactions of 1,6-enynes. Robust, chiral, and porous Zr-MOFs of UiO topology, BINAP-MOF (I) or BINAP-dMOF (II), were prepared using purely BINAP-derived dicarboxylate linkers or by mixing BINAP-derived linkers with unfunctionalized dicarboxylate linkers, respectively. Upon metalation with Rh(nbd)2BF4 and [Rh(nbd)Cl]2/AgSbF6, the MOF precatalysts I·Rh(BF4) and I·Rh(SbF6) efficiently catalyzed highly enantioselective (up to 99% ee) reductive cyclization and Alder-ene cycloisomerization of 1,6-enynes, respectively. I·Rh catalysts afforded cyclization products at comparable enantiomeric excesses (ee’s) and 4–7 times higher catalytic activity than the homogeneous controls, likely a result of catalytic site isolation in the MOF which prevents bimolecular catalyst deactivation pathways. However, I·Rh is inactive in the more sterically encumbered Pauson–Khand reactions between 1,6-enynes and carbon monoxide. In contrast, with a more open structure, Rh-functionalized BINAP-dMOF, II·Rh, effectively catalyzed Pauson–Khand cyclization reactions between 1,6-enynes and carbon monoxide at 10 times higher activity than the homogeneous control. II·Rh was readily recovered and used three times in Pauson–Khand cyclization reactions without deterioration of yields or ee’s. Our work has expanded the scope of MOF-catalyzed asymmetric reactions and showed that the mixed linker strategy can effectively enlarge the open space around the catalytic active site to accommodate highly sterically demanding polycyclic metallocycle transition states/intermediates in asymmetric intramolecular cyclization reactions.

  14. Metal-organic and zeolite imidazolate frameworks (MOFs and ZIFs) for highly selective separations

    Energy Technology Data Exchange (ETDEWEB)

    Yaghi, Omar M

    2012-09-17

    Metal-organic and zeolite imidazolate frameworks (MOFs and ZIFs) have been investigated for the realization as separation media with high selectivity. These structures are held together with strong bonds, making them architecturally, chemically, and thermally stable. Therefore, employing well designed building units, it is possible to discover promising materials for gas and vapor separation. This grant was focused on the study of MOFs and ZIFs with these specific objectives: (i) to develop a strategy for producing MOFs and ZIFs that combine high surface areas with active sites for their use in gas adsorption and separation of small organic compounds, (ii) to introduce active sites in the framework by a post-synthetic modification and metalation of MOFs and ZIFs, and (iii) to design and synthesize MOFs with extremely high surface areas and large pore volumes to accommodate large amounts of guest molecules. By the systematic study, this effort demonstrated how to introduce active functional groups in the frameworks, and this is also the origin of a new strategy, which is termed isoreticular functionalization and metalation. However, a large pore volume is still a prerequisite feature. One of the solutions to overcome this challenge is an isoreticular expansion of a MOF's structure. With triangular organic linker and square building units, we demonstrated that MOF-399 has a unit cell volume 17 times larger than that of the first reported material isoreticular to it, and it has the highest porosity (94%) and lowest density (0.126 g cm-3) of any MOF reported to date. MOFs are not just low density materials; the guest-free form of MOF-210 demonstrates an ultrahigh porosity, whose BET surface area was estimated to be 6240 m2 g-1 by N2 adsorption measurements.

  15. Understanding the H 2 Sorption Trends in the M-MOF-74 Series (M = Mg, Ni, Co, Zn)

    KAUST Repository

    Pham, Tony

    2015-01-15

    © 2014 American Chemical Society. Electronic structure calculations and simulations of H2 sorption were performed in four members of the M-MOF-74 series: Mg-MOF-74, Ni-MOF-74, Co-MOF-74, and Zn-MOF-74. Notable differences were observed in the partial charge and polarizability of the metal ions derived from the electronic structure calculations. The modeling parameters obtained from the electronic structure calculations were found to influence certain features in the experimentally observed H2 sorption trends in the M-MOF-74 series. The simulations were performed with the inclusion of explicit many-body polarization, which was required to reproduce the experimental H2 sorption observables (i.e., sorption isotherms and isosteric heats of adsorption (Qst)) and the H2-metal interaction in all four MOFs using classical molecular simulation. Consistent with experimental measurements, the simulations captured the following trend for the H2-metal interaction strength: Ni-MOF-74 > Co-MOF-74 > Mg-MOF-74 > Zn-MOF-74. The calculations revealed that stronger H2-metal interactions within the M-MOF-74 series corresponded to shorter H2-metal distances and higher induced dipoles on the metal-sorbed H2 molecules. In addition, it was observed that there was a strong correlation between the H2-metal interaction and the polarization contribution. Although Mg-MOF-74 has the highest calculated partial charge for the metal ion within the series, the Mg2+ ion has a very low polarizability compared to the other M2+ ions; this explains why the H2-metal interaction in this MOF is weaker compared to those for Ni-MOF-74 and Co-MOF-74. The sterics interactions, reflected in the crystal structure for all four MOFs, also played a role for the observed H2 sorption trends. Zn-MOF-74 has the lowest H2 uptakes and Qst within the series due to an unfavorable geometric environment for the Zn2+ ions within the ZnO5 clusters. Lastly, the two-dimensional quantum rotational levels were calculated for the H

  16. Preparation and Gas Adsorption of Porous Materials from Molecular Precursors

    DEFF Research Database (Denmark)

    Hu, Xinming

    and characteristics of various porous materials, including activated carbons, zeolites, metal-organic frameworks (MOFs), covalent organic frameworks (COFs), and organic porous polymers (POPs). Chapter 2 briefly introduces gas adsorption theory, such as physical and chemical adsorption, adsorption isotherms......), and H2 (2.0 wt%, 77 K and 1.0 bar). Chapters 5, 6, and 7 deal with the construction of triazatriangulenium (TATA)-based ionic porous frameworks. A variety of polycondensation reactions have been applied, but only FeCl3-promoted oxidative polymerization of thiophene-/carbazolefunctionalized TATAs...... rise to significant red-shift of absorption/emission and reduction of fluorescence lifetime and quantum yield Transition-metal-catalyzed and organolithium-mediated reactions provide polymers with only macroporous interparticle voids and thus very low surface areas (4−51 m2 g−1). Attempts have been also...

  17. Linker Installation: Engineering Pore Environment with Precisely Placed Functionalities in Zirconium MOFs.

    Science.gov (United States)

    Yuan, Shuai; Chen, Ying-Pin; Qin, Jun-Sheng; Lu, Weigang; Zou, Lanfang; Zhang, Qiang; Wang, Xuan; Sun, Xing; Zhou, Hong-Cai

    2016-07-20

    Precise placement of multiple functional groups in a highly ordered metal-organic framework (MOF) platform allows the tailoring of the pore environment, which is required for advanced applications. To realize this, we present a comprehensive study on the linker installation method, in which a stable MOF with coordinatively unsaturated Zr6 clusters was employed and linkers bearing different functional groups were postsynthetically installed. A Zr-MOF with inherent missing linker sites, namely, PCN-700, was initially constructed under kinetic control. Twelve linkers with different substituents were then designed to study their effect on MOF formation kinetics and therefore resulting MOF structures. Guided by the geometrical analysis, linkers with different lengths were installed into a parent PCN-700, giving rise to 11 new MOFs and each bearing up to three different functional groups in predefined positions. Systematic variation of the pore volume and decoration of pore environment were realized by linker installation, which resulted in synergistic effects including an enhancement of H2 adsorption capacities of up to 57%. In addition, a size-selective catalytic system for aerobic alcohol oxidation reaction is built in PCN-700 through linker installation, which shows high activity and tunable size selectivity. Altogether, these results exemplify the capability of the linker installation method in the pore environment engineering of stable MOFs with multiple functional groups, giving an unparalleled level of control. PMID:27345035

  18. MOF phosphorylation by ATM regulates 53BP1-mediated DSB repair pathway choice

    Science.gov (United States)

    Gupta, Arun; Hunt, Clayton R.; Hegdec, Muralidhar L.; Chakraborty, Sharmistha; Udayakumar, Durga; Horikoshi, Nobuo; Singh1, Mayank; Ramnarain, Deepti B.; Hittelman, Walter N.; Namjoshi, Sarita; Asaithamby, Aroumougame; Hazra, Tapas K.; Ludwig, Thomas; Pandita, Raj K.; Tyler, Jessica K.; Pandita, Tej K.

    2014-01-01

    Cell cycle phase is a critical determinant of the choice between DNA damage repair by non-homologous end joining (NHEJ) or homologous recombination (HR). Here we report that DSBs induce ATM-dependent MOF (a histone H4 acetyl-transferase) phosphorylation (p-T392-MOF) and that phosphorylated MOF co-localizes with γ-H2AX, ATM, and 53BP1 foci. Mutation of the phosphorylation site (MOF-T392A) impedes DNA repair in S- and G2-phase but not G1-phase cells. Expression of MOF-T392A also reverses the reduction in DSB associated 53BP1 seen in wild type S/G2-phase cells, resulting in enhanced 53BP1 and reduced BRCA1 association. Decreased BRCA1 levels at DSB sites correlates with defective repairosome formation, reduced HR repair and decreased cell survival following irradiation. These data support a model whereby ATM mediated MOF-T392 phosphorylation modulates 53BP1 function to facilitate the subsequent recruitment of HR repair proteins, uncovering a regulatory role for MOF in DSB repair pathway choice during S/G2-phase. PMID:24953651

  19. MOF Phosphorylation by ATM Regulates 53BP1-Mediated Double-Strand Break Repair Pathway Choice

    Directory of Open Access Journals (Sweden)

    Arun Gupta

    2014-07-01

    Full Text Available Cell-cycle phase is a critical determinant of the choice between DNA damage repair by nonhomologous end-joining (NHEJ or homologous recombination (HR. Here, we report that double-strand breaks (DSBs induce ATM-dependent MOF (a histone H4 acetyl-transferase phosphorylation (p-T392-MOF and that phosphorylated MOF colocalizes with γ-H2AX, ATM, and 53BP1 foci. Mutation of the phosphorylation site (MOF-T392A impedes DNA repair in S and G2 phase but not G1 phase cells. Expression of MOF-T392A also blocks the reduction in DSB-associated 53BP1 seen in wild-type S/G2 phase cells, resulting in enhanced 53BP1 and reduced BRCA1 association. Decreased BRCA1 levels at DSB sites correlates with defective repairosome formation, reduced HR repair, and decreased cell survival following irradiation. These data support a model whereby ATM-mediated MOF-T392 phosphorylation modulates 53BP1 function to facilitate the subsequent recruitment of HR repair proteins, uncovering a regulatory role for MOF in DSB repair pathway choice during S/G2 phase.

  20. Partitioning MOF-5 into Confined and Hydrophobic Compartments for Carbon Capture under Humid Conditions.

    Science.gov (United States)

    Ding, Nan; Li, Haiwei; Feng, Xiao; Wang, Qianyou; Wang, Shan; Ma, Li; Zhou, Junwen; Wang, Bo

    2016-08-17

    Metal-organic frameworks (MOFs), by virtue of their remarkable uptake capability, selectivity, and ease of regeneration, hold great promise for carbon capture from fossil fuel combustion. However, their stability toward moisture together with the competitive adsorption of water against CO2 drastically dampens their capacity and selectivity under real humid flue gas conditions. In this work, an effective strategy was developed to tackle the above obstacles by partitioning the channels of MOFs into confined, hydrophobic compartments by in situ polymerization of aromatic acetylenes. Specifically, polynaphthylene was formed via a radical reaction inside the channels of MOF-5 and served as partitions without altering the underlying structure of the framework. Compared with pristine MOF-5, the resultant material (PN@MOF-5) exhibits a doubled CO2 capacity (78 vs 38 cm(3)/g at 273 K and 1 bar), 23 times higher CO2/N2 selectivity (212 vs 9), and significantly improved moisture stability. The dynamic CO2 adsorption capacity can be largely maintained (>90%) under humid conditions during cycles. This strategy can be applied to other MOF materials and may shed light on the design of new MOF-polymer materials with tunable pore sizes and environments to promote their practical applications. PMID:27477091

  1. Partitioning MOF-5 into Confined and Hydrophobic Compartments for Carbon Capture under Humid Conditions.

    Science.gov (United States)

    Ding, Nan; Li, Haiwei; Feng, Xiao; Wang, Qianyou; Wang, Shan; Ma, Li; Zhou, Junwen; Wang, Bo

    2016-08-17

    Metal-organic frameworks (MOFs), by virtue of their remarkable uptake capability, selectivity, and ease of regeneration, hold great promise for carbon capture from fossil fuel combustion. However, their stability toward moisture together with the competitive adsorption of water against CO2 drastically dampens their capacity and selectivity under real humid flue gas conditions. In this work, an effective strategy was developed to tackle the above obstacles by partitioning the channels of MOFs into confined, hydrophobic compartments by in situ polymerization of aromatic acetylenes. Specifically, polynaphthylene was formed via a radical reaction inside the channels of MOF-5 and served as partitions without altering the underlying structure of the framework. Compared with pristine MOF-5, the resultant material (PN@MOF-5) exhibits a doubled CO2 capacity (78 vs 38 cm(3)/g at 273 K and 1 bar), 23 times higher CO2/N2 selectivity (212 vs 9), and significantly improved moisture stability. The dynamic CO2 adsorption capacity can be largely maintained (>90%) under humid conditions during cycles. This strategy can be applied to other MOF materials and may shed light on the design of new MOF-polymer materials with tunable pore sizes and environments to promote their practical applications.

  2. A Review on Breathing Behaviors of Metal-Organic-Frameworks (MOFs for Gas Adsorption

    Directory of Open Access Journals (Sweden)

    Mays Alhamami

    2014-04-01

    Full Text Available Metal-organic frameworks (MOFs are a new class of microporous materials that possess framework flexibility, large surface areas, “tailor-made” framework functionalities, and tunable pore sizes. These features empower MOFs superior performances and broader application spectra than those of zeolites and phosphine-based molecular sieves. In parallel with designing new structures and new chemistry of MOFs, the observation of unique breathing behaviors upon adsorption of gases or solvents stimulates their potential applications as host materials in gas storage for renewable energy. This has attracted intense research energy to understand the causes at the atomic level, using in situ X-ray diffraction, calorimetry, Fourier transform infrared spectroscopy, and molecular dynamics simulations. This article is developed in the following order: first to introduce the definition of MOFs and the observation of their framework flexibility. Second, synthesis routes of MOFs are summarized with the emphasis on the hydrothermal synthesis, owing to the environmental-benign and economically availability of water. Third, MOFs exhibiting breathing behaviors are summarized, followed by rationales from thermodynamic viewpoint. Subsequently, effects of various functionalities on breathing behaviors are appraised, including using post-synthetic modification routes. Finally, possible framework spatial requirements of MOFs for yielding breathing behaviors are highlighted as the design strategies for new syntheses.

  3. Nanoscale Synthesis of Two Porphyrin-Based MOFs with Gallium and Indium.

    Science.gov (United States)

    Rhauderwiek, Timo; Waitschat, Steve; Wuttke, Stefan; Reinsch, Helge; Bein, Thomas; Stock, Norbert

    2016-06-01

    Two porphyrin-based metal-organic frameworks (MOFs) containing gallium or indium, [Ga2(OH)2(H2TCPP)]·3DMF·3H2O (Ga-PMOF) and [In2(OH)2(H2TCPP)]·3DMF·4H2O (In-PMOF) (H6TCPP = 4-tetracarboxyphenylporphyrin), were discovered using high-throughput methods. The structure was refined by the Rietveld-method starting from the structure model of Al-PMOF, [Al2(OH)2(H2TCPP)]. The new PMOFs exhibit BET surface areas between 1150 and 1400 m(2) g(-1) and are also porous toward CO2 (Ga-PMOF, 15.2 wt %; In-PMOF, 12.9 wt %). They are thermally stable in air up to 330 °C, but show limited chemical stabilities toward acids and bases. In order to achieve size control, different synthesis routes were investigated, i.e., batch synthesis at different temperatures (yield: In-PMOF-bs-th 96%, Ga-PMOF-bs-th 87%), ultrasound-assisted synthesis (yield: In-PMOF-bs-us 85%), and continuous-flow synthesis (yield: Ga-PMOF-cf 71%). By using these different methods we could control the nucleation rate and the crystal size. The crystal sizes were found to vary about 60 to 160 nm and 70 to 130 nm for Ga- and In-PMOF, respectively, which was proven by dynamic light scattering (DLS), powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) measurements.

  4. Observation of single-file diffusion in a MOF.

    Science.gov (United States)

    Jobic, H

    2016-06-29

    The translational and rotational dynamics of neopentane adsorbed in the one-dimensional channels of MIL-47(V) has been studied by quasi-elastic neutron scattering. The rotational motion of neopentane is well-described by the rotational diffusion model, with a correlation time of 41 ps at 300 K. The translational motion of the molecule has been fitted by several models: isotropic diffusion, normal 1D and single-file diffusion. It is found that the observed line shapes can only be reproduced by the single-file diffusion model. The single-file mobility factor, F, is (8 ± 1) × 10(-14) m(2) s(-1/2) at 300 K. This is the first observation of this unusual diffusion behaviour in a MOF. PMID:26932296

  5. Bio-inspired MOF-based Catalysts for Lignin Valorization.

    Energy Technology Data Exchange (ETDEWEB)

    Allendorf, Mark D.; Stavila, Vitalie; Ramakrishnan, Parthasarathi; Davis, Ryan Wesley

    2014-09-01

    Lignin is a potentially plentiful source of renewable organics, with %7E50Mtons/yr produced by the pulp/paper industry and 200-300 Mtons/yr projected production by a US biofuels industry. This industry must process approximately 1 billion tons of biomass to meet the US Renewable Fuel goals. However, there are currently no efficient processes for converting lignin to value-added chemicals and drop-in fuels. Lignin is therefore an opportunity for production of valuable renewable chemicals, but presents staggering technical and economic challenges due to the quantities of material involved and the strong chemical bonds comprising this polymer. Aggressive chemistries and high temperatures are required to degrade lignin without catalysts. Moreover, chemical non-uniformity among lignins leads to complex product mixtures that tend to repolymerize. Conventional petrochemical approaches (pyrolysis, catalytic cracking, gasification) are energy intensive (400-800 degC), require complicated separations, and remove valuable chemical functionality. Low-temperature (25-200 degC) alternatives are clearly desirable, but enzymes are thermally fragile and incompatible with liquid organic compounds, making them impractical for large-scale biorefining. Alternatively, homogeneous catalysts, such as recently developed vanadium complexes, must be separated from product mixtures, while many heterogenous catalysts involve costly noble metals. The objective of this project is to demonstrate proof of concept that an entirely new class of biomimetic, efficient, and industrially robust synthetic catalysts based on nanoporous Metal- Organic Frameworks (MOFs) can be developed. Although catalytic MOFs are known, catalysis of bond cleavage reactions needed for lignin degradation is completely unexplored. Thus, fundamental research is required that industry and most sponsoring agencies are currently unwilling to undertake. We introduce MOFs infiltrated with titanium and nickel species as catalysts

  6. Carbon dioxide capturing technologies: a review focusing on metal organic framework materials (MOFs).

    Science.gov (United States)

    Sabouni, Rana; Kazemian, Hossein; Rohani, Sohrab

    2014-04-01

    In this study, a relevant literature has been reviewed focusing on the carbon dioxide capture technologies in general, such as amine-based absorption as conventional carbon dioxide capturing technology, aqueous ammonia-based absorption, membranes, and adsorption material (e.g., zeolites, and activated carbons). In more details, metal organic frameworks (MOFs) as new emerging technologies for carbon dioxide adsorption are discussed. The MOFs section is intended to provide a comprehensive overview of MOFs including material characteristics and synthesis, structural features, CO2 adsorption capacity, heat of adsorption and selectivity of CO2. PMID:24338107

  7. Molecular Simulation Studies of Flue Gas Purification by Bio-MOF

    OpenAIRE

    Zhi Li; Gangqiang Xu; Bei Liu; Xin Lv; Guangjin Chen; Changyu Sun; Peng Xiao; Yifei Sun

    2015-01-01

    As a new branch of MOFs which are composed of biocompatible metal ions and organic ligands, bio-metal-organic frameworks (bio-MOFs) have attracted much attention recently. Bio-MOFs feature multiple Lewis basic sites which have strong interaction with CO2 molecules, thus they have great potential in the separation and purification of gas mixtures containing CO2. In this work, molecular simulation studies were carried out to investigate the adsorption and diffusion behaviors of CO2/N2 gas mixtu...

  8. Synthesis and hydrogen-storage behavior of metal-organic framework MOF-5

    Energy Technology Data Exchange (ETDEWEB)

    Li, Jinping; Zhao, Qiang; Long, Peipei; Dong, Jinxiang [Research Institute of Special Chemicals, Taiyuan University of Technology, Taiyuan 030024, Shanxi (China); Cheng, Shaojuan [Department of Environmental and Chemical Engineering, Luoyang Institute of Science and Technology, Luoyang, Henan 471023 (China)

    2009-02-15

    Metal-organic framework MOF-5 (Zn{sub 4}O(BDC){sub 3}), a microporous material with a high surface area and large pore volume, was synthesized by three approaches: direct mixing of triethylamine (TEA), slow diffusion of TEA, and solvothermal synthesis. The obtained materials were characterized by X-ray diffraction, scanning electron microscopy, thermogravimetric analysis, and nitrogen adsorption, and their hydrogen-storage capacities were measured. The different synthesis methods influenced the pore-structure parameters, morphologies and hydrogen-storage behavior of the obtained MOF-5. MOF-5 synthesized by the solvothermal approach showed a higher surface area and larger pore volume than the samples prepared by the other two approaches. Measurements of the hydrogen-storage behavior showed that the hydrogen-storage capacity was correlated with the specific surface area and pore volume of MOF-5. (author)

  9. Gas adsorption and gas mixture separations using mixed-ligand MOF material

    Science.gov (United States)

    Hupp, Joseph T.; Mulfort, Karen L.; Snurr, Randall Q.; Bae, Youn-Sang

    2011-01-04

    A method of separating a mixture of carbon dioxiode and hydrocarbon gas using a mixed-ligand, metal-organic framework (MOF) material having metal ions coordinated to carboxylate ligands and pyridyl ligands.

  10. Synthesis and CO{sub 2} adsorption study of modified MOF-5 with multi-wall carbon nanotubes and expandable graphite

    Energy Technology Data Exchange (ETDEWEB)

    Ullah, Sami, E-mail: samichemist1@gmail.com, E-mail: azmibustam@petronas.com.my, E-mail: azmish@petronas.com.my, E-mail: lkhlfh@gmail.com, E-mail: hmurshid@gmail.com, E-mail: nadiariazz@gmail.com; Bustam, M. A., E-mail: samichemist1@gmail.com, E-mail: azmibustam@petronas.com.my, E-mail: azmish@petronas.com.my, E-mail: lkhlfh@gmail.com, E-mail: hmurshid@gmail.com, E-mail: nadiariazz@gmail.com; Shariff, A. M., E-mail: samichemist1@gmail.com, E-mail: azmibustam@petronas.com.my, E-mail: azmish@petronas.com.my, E-mail: lkhlfh@gmail.com, E-mail: hmurshid@gmail.com, E-mail: nadiariazz@gmail.com; Elkhalifah, Ali E. I., E-mail: samichemist1@gmail.com, E-mail: azmibustam@petronas.com.my, E-mail: azmish@petronas.com.my, E-mail: lkhlfh@gmail.com, E-mail: hmurshid@gmail.com, E-mail: nadiariazz@gmail.com; Murshid, G., E-mail: samichemist1@gmail.com, E-mail: azmibustam@petronas.com.my, E-mail: azmish@petronas.com.my, E-mail: lkhlfh@gmail.com, E-mail: hmurshid@gmail.com, E-mail: nadiariazz@gmail.com; Riaz, Nadia, E-mail: samichemist1@gmail.com, E-mail: azmibustam@petronas.com.my, E-mail: azmish@petronas.com.my, E-mail: lkhlfh@gmail.com, E-mail: hmurshid@gmail.com, E-mail: nadiariazz@gmail.com [Research Center for Carbon Dioxide Capture, Dept. of Chemical Engineering, Universiti Teknologi PETRONAS, Bandar Sri Iskandar, Tronoh 31750 Perak (Malaysia)

    2014-10-24

    MOF-5 was synthesized by solvothermal method and its reactivation under anhydrous conditions. This research is conducted to investigate the effect of MOF-5 and MOF-5 modified with multi-wall carbon nanotubes (MWCNTs) and expandable graphite (EG) on the performance of CO{sub 2} adsorption. The synthesized MOFs were characterized using Field emission scanning electron microscopy (FESEM) for surface morphology, Thermogravimetric analysis (TGA) for thermal stability, X-ray diffraction (XRD) for crystals plane, Brunauer-Emmet-Teller (BET) for surface area and CO{sub 2} adsorption. The result had showed that the modified MOF-5 enhanced the CO{sub 2} adsorption compared to the pure MOF-5. The increment in the CO{sub 2} uptake capacities of MOF materials was attributed to the decrease in the pore size and enhancement of micropore volume of MOF-5 by multi-walled carbon nanotube and EG incorporation. The BET surface area of the synthesized MOF-5@MWCNTs is more than MOF-5. The CO{sub 2} sorption capacities of MOF-5 and MOF-5@MWCNTs were observed to increase from 0.00008 to 0.00048 mol g-1 at 298 K and 1 bar. The modified MOF-5@MWCNTs resulted in the highest CO{sub 2} adsorption followed by the modified MOF-5@ EG and lastly, MOF-5.

  11. Porous coordination polymers as novel sorption materials for heat transformation processes.

    Science.gov (United States)

    Janiak, Christoph; Henninger, Stefan K

    2013-01-01

    Porous coordination polymers (PCPs)/metal-organic frameworks (MOFs) are inorganic-organic hybrid materials with a permanent three-dimensional porous metal-ligand network. PCPs or MOFs are inorganic-organic analogs of zeolites in terms of porosity and reversible guest exchange properties. Microporous water-stable PCPs with high water uptake capacity are gaining attention for low temperature heat transformation applications in thermally driven adsorption chillers (TDCs) or adsorption heat pumps (AHPs). TDCs or AHPs are an alternative to traditional air conditioners or heat pumps operating on electricity or fossil fuels. By using solar or waste heat as the operating energy TDCs or AHPs can significantly help to minimize primary energy consumption and greenhouse gas emissions generated by industrial or domestic heating and cooling processes. TDCs and AHPs are based on the evaporation and consecutive adsorption of coolant liquids, preferably water, under specific conditions. The process is driven and controlled by the microporosity and hydrophilicity of the employed sorption material. Here we summarize the current investigations, developments and possibilities of PCPs/MOFs for use in low-temperature heat transformation applications as alternative materials for the traditional inorganic porous substances like silica gel, aluminophosphates or zeolites. PMID:23945102

  12. Identifying Highly Selective MOFs for CH4/H2 Separations using Computational Tools

    OpenAIRE

    Başdoğan, Yasemin; Sezginel, Kutay Berk; Keskin Avcı, Seda

    2015-01-01

    The large number of metal organic frameworks (MOFs) represents both an opportunity and a challenge for identification of materials exhibiting promising properties in gas separations. We used molecular simulations to screen 250 different MOP structures in order to examine their adsorption-based CH4/H-2 separation performances. Adsorption selectivity, working capacity, sorbent selection parameter, and regenerability of MOFs were calculated and compared with those of traditional nanoporous mater...

  13. The DeNOx process and NO2 adsorption in MOF74

    Science.gov (United States)

    Zuluaga, S.; Thonhauser, T.; Tan, K.; Chabal, Y.

    2014-03-01

    Due to the harmful character of NO2 and its slow decomposition rate, the use of catalytic materials for its removal (DeNOx process) has attracted a lot of attention. The high porosity and highly reactive uncoordinated metal centers of MOF74 have led us to investigate the use of Mg- and Zn-MOF74 as materials for trapping NO2 with resistance to poisoning by SO2. In this combined theoretical and experimental study, we investigate the interaction between the unsaturated metal centers of the MOF and the NO2 guest molecules. For our theoretical modeling we use ab initio calculations at the DFT level, utilizing vdW-DF to capture the significant van der Waals component of the interaction between NO2 and the MOF. We present detailed first-principle results concerning the adsorption energies and geometries, as well as vibration frequencies of the NO2 molecule adsorbed in the MOF. Our experimental efforts (IR and Raman spectroscopy) have shown a blue shift to 1684 cm-1 in the vibration stretching mode of the NO2 upon adsorption and a thermal stability up to 150°C. Our first-principle calculations and experimental results show a remarkable agreement, allowing us to give a complete picture of the adsorption of NO2 molecules in the MOF74 structure. Supported by DOE DE-FG02-08ER46491.

  14. MOF Acetylates the Histone Demethylase LSD1 to Suppress Epithelial-to-Mesenchymal Transition.

    Science.gov (United States)

    Luo, Huacheng; Shenoy, Anitha K; Li, Xuehui; Jin, Yue; Jin, Lihua; Cai, Qingsong; Tang, Ming; Liu, Yang; Chen, Hao; Reisman, David; Wu, Lizi; Seto, Edward; Qiu, Yi; Dou, Yali; Casero, Robert A; Lu, Jianrong

    2016-06-21

    The histone demethylase LSD1 facilitates epithelial-to-mesenchymal transition (EMT) and tumor progression by repressing epithelial marker expression. However, little is known about how its function may be modulated. Here, we report that LSD1 is acetylated in epithelial but not mesenchymal cells. Acetylation of LSD1 reduces its association with nucleosomes, thus increasing histone H3K4 methylation at its target genes and activating transcription. The MOF acetyltransferase interacts with LSD1 and is responsible for its acetylation. MOF is preferentially expressed in epithelial cells and is downregulated by EMT-inducing signals. Expression of exogenous MOF impedes LSD1 binding to epithelial gene promoters and histone demethylation, thereby suppressing EMT and tumor invasion. Conversely, MOF depletion enhances EMT and tumor metastasis. In human cancer, high MOF expression correlates with epithelial markers and a favorable prognosis. These findings provide insight into the regulation of LSD1 and EMT and identify MOF as a critical suppressor of EMT and tumor progression. PMID:27292636

  15. MOF Acetylates the Histone Demethylase LSD1 to Suppress Epithelial-to-Mesenchymal Transition

    Directory of Open Access Journals (Sweden)

    Huacheng Luo

    2016-06-01

    Full Text Available The histone demethylase LSD1 facilitates epithelial-to-mesenchymal transition (EMT and tumor progression by repressing epithelial marker expression. However, little is known about how its function may be modulated. Here, we report that LSD1 is acetylated in epithelial but not mesenchymal cells. Acetylation of LSD1 reduces its association with nucleosomes, thus increasing histone H3K4 methylation at its target genes and activating transcription. The MOF acetyltransferase interacts with LSD1 and is responsible for its acetylation. MOF is preferentially expressed in epithelial cells and is downregulated by EMT-inducing signals. Expression of exogenous MOF impedes LSD1 binding to epithelial gene promoters and histone demethylation, thereby suppressing EMT and tumor invasion. Conversely, MOF depletion enhances EMT and tumor metastasis. In human cancer, high MOF expression correlates with epithelial markers and a favorable prognosis. These findings provide insight into the regulation of LSD1 and EMT and identify MOF as a critical suppressor of EMT and tumor progression.

  16. Porous carbons

    Indian Academy of Sciences (India)

    Satish M Manocha

    2003-02-01

    Carbon in dense as well as porous solid form is used in a variety of applications. Activated porous carbons are made through pyrolysis and activation of carbonaceous natural as well as synthetic precursors. Pyrolysed woods replicate the structure of original wood but as such possess very low surface areas and poor adsorption capacities. On activation, these exhibit increased adsorption volumes of 0.5–0.8 cm3 /gm and surface areas of 700–1800 m2 /gm depending on activation conditions, whether physical or chemical. Former carbons possess mixed pore size distribution while chemically activated carbons predominantly possess micropores. Thus, these carbons can be used for adsorption of wide distributions of molecules from gas to liquid. The molecular adsorption within the pores is due to single layer or multilayer molecule deposition at the pore walls and hence results in different types of adsorption isotherm. On the other hand, activated carbon fibres with controlled microporous structure and surface area in the range of 2500 m2 /gm can be developed by controlled pyrolysis and physical activation of amorphous carbon fibres. Active carbon fibres with unmatchable pore structure and surface characteristics are present and futuristic porous materials for a number of applications from pollution control to energy storage.

  17. Robustness and Thermophysical Properties of MOF-5: A Prototypical Hydrogen Storage Material

    Science.gov (United States)

    Ming, Yang

    Metal-organic frameworks (MOFs) are an emerging class of microporous, crystalline materials with potential applications in the capture, storage, and separation of gasses. Of the many known MOFs, the compound known as MOF-5 has attracted considerable attention due to its ability to store gaseous fuels at low pressure with high densities. However, low thermal conductivity and limited robustness upon exposure to water and other reactive species are two challenges which limit the application of MOF-5; similar issues plague several other MOFs. The focus of this dissertation is to understand and overcome these shortcomings through detailed experimental and computational characterization of the prototype compound, MOF-5. The insight provided by this study regarding the properties of MOFs will aid in the transition of these materials from lab bench to applications. Improvements to the thermal conductivity of MOF-5 are demonstrated using densified pellets consisting of a physical mixture of MOF-5 and expanded natural graphite (ENG). The high-aspect ratio of ENG particles, combined with uni-axial compression, results in anisotropic microstructural and thermal transport properties in the pellets. Perpendicular to the pressing direction the thermal conductivity was observed to be two to four times higher than in the orthogonal direction. We further demonstrate that this anisotropy can be exploited to enhance conductivity along a preferred direction in the pellets by altering the pellet processing conditions. We conclude that the low thermal conductivity typical of MOFs can be improved using a judicious combination of second phase additions and processing techniques. Regarding robustness, we first quantify experimentally the impact of humid air exposure on the properties of MOF-5 as a function of exposure time, humidity level, and morphology (i.e., powders vs. pellets). For humidity levels below 50% only minor degradation is observed for exposure times up to several hours. In

  18. Microwave-assisted modulated synthesis of zirconium-based metal-organic framework (Zr-MOF) for hydrogen storage applications

    Energy Technology Data Exchange (ETDEWEB)

    Ren, Jianwei; Segakweng, Tshiamo; Langmi, Henrietta W.; Musyoka, Nicholas M.; North, Brian C.; Mathe, Mkhulu [Council for Scientific and Industrial Research (CSIR), Pretoria (South Africa). HySA Infrastructure Centre of Competence, Materials Science and Manufacturing; Bessarabov, Dmitri [North-West Univ. (NWU), Potchefstroom (South Africa). HySA Infrastructure Centre of Competence

    2014-05-15

    Zirconium-based metal-organic framework (Zr-MOF) was synthesized using a microwave-assisted modulated method in a short reaction time of 5 min. The Zr-MOF material was highly crystalline with well-defined octahedral shaped crystals, and it exhibited comparable hydrogen storage capacity to Zr-MOF of similar specific surface area synthesized using conventional methods with much longer synthesis time. (orig.)

  19. Thermodynamics of solvent interaction with the metal-organic framework MOF-5.

    Science.gov (United States)

    Akimbekov, Zamirbek; Wu, Di; Brozek, Carl K; Dincă, Mircea; Navrotsky, Alexandra

    2016-01-14

    The inclusion of solvent in metal-organic framework (MOF) materials is a highly specific form of guest-host interaction. In this work, the energetics of solvent MOF-5 interactions has been investigated by solution calorimetry in 5 M sodium hydroxide (NaOH) at room temperature. Solution calorimetric measurement of enthalpy of formation (ΔH(f)) of Zn4O(C8H4O4)3·C3H7NO (MOF-5·DMF) and Zn4O(C8H4O4)3·0.60C5H11NO (MOF-5·0.60DEF) from the dense components zinc oxide (ZnO), 1,4-benzenedicarboxylic acid (H2BDC), N,N-dimethylformamide (DMF) and N,N-diethylformamide (DEF) gives values of 16.69 ± 1.21 and 45.90 ± 1.46 kJ (mol Zn4O)(-1), respectively. The enthalpies of interaction (ΔH(int)) for DMF and DEF with MOF-5 are -82.78 ± 4.84 kJ (mol DMF)(-1) and -89.28 ± 3.05 kJ (mol DEF)(-1), respectively. These exothermic interaction energies suggest that, at low guest loading, Lewis base solvents interact more strongly with electron accepting Zn4O clusters in the MOF than at high solvent loading. These data provide a quantitative thermodynamic basis to investigate transmetallation and solvent assisted linker exchange (SALE) methods and to synthesize new MOFs. PMID:26658672

  20. Development and Test Evaluations for Ni-DOBDC Metal Organic Framework (MOF) Engineered Forms

    Energy Technology Data Exchange (ETDEWEB)

    Troy G. Garn; Mitchell Greenhalgh

    2013-07-01

    A joint effort to prepare engineered forms of a Ni-DOBDC metal organic framework (MOF) was completed with contributions from PNNL, SNL and the INL. Two independent methods were used at INL and SNL to prepare engineered form (EF) sorbents from Ni-DOBDC MOF powder developed and prepared at PNNL. Xe and Kr capacity test evaluations were performed at ambient temperature with the cryostat experimental setup at INL. The initial INL EF MOF test results indicated a Xe capacity of 1.6 mmol/kg sorbent and no Kr capacity. A large loss of surface area also occurred during minimal testing rendering the INL EF MOF unusable. Four capacity tests were completed using the SNL EF MOF at ambient temperature and resulted in Xe capacities of 1.4, 4.2, 5.0 and 3.8 mmol/kg sorbent with no Kr capacity observed in any ambient temperature tests. Two additional capacity tests were performed at 240 K to further evaluate SNL EF MOF performance. Xe capacities of 50.7 and 49.3 mmol/kg of sorbent and Kr capacities of 0.77 and 0.69 mmol/kg of sorbent were obtained, respectively. Following the adsorption evaluations, the SNL EF MOF material had lost about 40 % of the initial mass and 40 % of the initial surface area. In general, the Xe capacity results at ambient temperature for the INL and SNL EF Ni-DOBDC MOF’s were lower than 9.8 mmol Xe/kg sorbent test results reported by INL in FY-12 using PNNL’s inital EF supplied material.

  1. Hydrogen-Bonded Organic Frameworks (HOFs): A New Class of Porous Crystalline Proton-Conducting Materials.

    Science.gov (United States)

    Karmakar, Avishek; Illathvalappil, Rajith; Anothumakkool, Bihag; Sen, Arunabha; Samanta, Partha; Desai, Aamod V; Kurungot, Sreekumar; Ghosh, Sujit K

    2016-08-26

    Two porous hydrogen-bonded organic frameworks (HOFs) based on arene sulfonates and guanidinium ions are reported. As a result of the presence of ionic backbones appended with protonic source, the compounds exhibit ultra-high proton conduction values (σ) 0.75× 10(-2)  S cm(-1) and 1.8×10(-2)  S cm(-1) under humidified conditions. Also, they have very low activation energy values and the highest proton conductivity at ambient conditions (low humidity and at moderate temperature) among porous crystalline materials, such as metal-organic frameworks (MOFs) and covalent organic frameworks (COFs). These values are not only comparable to the conventionally used proton exchange membranes, such as Nafion used in fuel cell technologies, but is also the highest value reported in organic-based porous architectures. Notably, this report inaugurates the usage of crystalline hydrogen-bonded porous organic frameworks as solid-state proton conducting materials. PMID:27464784

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

    Directory of Open Access Journals (Sweden)

    Adrián Angulo-Ibáñez

    2016-01-01

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

  3. Metal-Organic Frameworks Derived Porous Core/Shell Structured ZnO/ZnCo2O4/C Hybrids as Anodes for High-Performance Lithium-Ion Battery.

    Science.gov (United States)

    Ge, Xiaoli; Li, Zhaoqiang; Wang, Chengxiang; Yin, Longwei

    2015-12-01

    Metal-organic frameworks (MOFs) derived porous core/shell ZnO/ZnCo2O4/C hybrids with ZnO as a core and ZnCo2O4 as a shell are for the first time fabricated by using core/shell ZnCo-MOF precursors as reactant templates. The unique MOFs-derived core/shell structured ZnO/ZnCo2O4/C hybrids are assembled from nanoparticles of ZnO and ZnCo2O4, with homogeneous carbon layers coated on the surface of the ZnCo2O4 shell. When acting as anode materials for lithium-ion batteries (LIBs), the MOFs-derived porous ZnO/ZnCo2O4/C anodes exhibit outstanding cycling stability, high Coulombic efficiency, and remarkable rate capability. The excellent electrochemical performance of the ZnO/ZnCo2O4/C LIB anodes can be attributed to the synergistic effect of the porous structure of the MOFs-derived core/shell ZnO/ZnCo2O4/C and homogeneous carbon layer coating on the surface of the ZnCo2O4 shells. The hierarchically porous core/shell structure offers abundant active sites, enhances the electrode/electrolyte contact area, provides abundant channels for electrolyte penetration, and also alleviates the structure decomposition induced by Li(+) insertion/extraction. The carbon layers effectively improve the conductivity of the hybrids and thus enhance the electron transfer rate, efficiently prevent ZnCo2O4 from aggregation and disintegration, and partially buffer the stress induced by the volume change during cycles. This strategy may shed light on designing new MOF-based hybrid electrodes for energy storage and conversion devices.

  4. Capturing the H 2 –Metal Interaction in Mg-MOF-74 Using Classical Polarization

    KAUST Repository

    Pham, Tony

    2014-10-02

    © 2014 American Chemical Society. Grand canonical Monte Carlo (GCMC) simulations of H2 sorption were performed in Mg-MOF-74, a metal-organic framework (MOF) that displays very high H2 sorption affinity. Experimental H2 sorption isotherms and isosteric heats of adsorption (Qst) values were reproduced using a general purpose materials sorption potential that includes many-body polarization interactions. In contrast, using two models that include only charge-quadrupole interactions failed to reproduce such experimental measurements even though they are the type normally employed in such classical force field calculations. Utilizing the present explicit polarizable model in GCMC simulation resulted in a Mg2+-H2 distance of 2.60 Å, which is close to a previously reported value that was obtained using electronic structure methods and comparable to similar experimental measurements. The induced dipole distribution obtained from simulation assisted in the characterization of two previously identified sorption sites in the MOF: the Mg2+ ions and the oxido group of the linkers. The calculated two-dimensional quantum rotational levels for a H2 molecule sorbed onto the Mg2+ ion were in good agreement with experimental inelastic neutron scattering (INS) data. Although the H2-metal interaction in MOFs may be thought of as a quantum mechanical effect, this study demonstrates how the interaction between the sorbate molecules and the open-metal sites in a particular highly sorbing MOF can be captured using classical simulation techniques that involve a polarizable potential.

  5. ZIF-Derived Nitrogen-Doped Porous Carbons for Xe Adsorption and Separation

    Science.gov (United States)

    Zhong, Shan; Wang, Qian; Cao, Dapeng

    2016-02-01

    Currently, finding high capacity adsorbents with large selectivity to capture Xe is still a great challenge. In this work, nitrogen-doped porous carbons were prepared by programmable temperature carbonization of zeolitic imidazolate framework-8 (ZIF-8) and ZIF-8/xylitol composite precursors and the resultant samples are marked as Carbon-Z and Carbon-ZX, respectively. Further adsorption measurements indicate that ZIF-derived nitrogen-doped Carbon-ZX exhibits extremely high Xe capacity of 4.42 mmol g-1 at 298 K and 1 bar, which is higher than almost all other pristine MOFs such as CuBTC, Ni/DOBDC, MOF-5 and Al-MIL-53, and even more than three times of the matrix ZIF-8 at similar conditions. Moreover, Carbon-ZX also shows the highest Xe/N2 selectivity about ~120, which is much larger than all other reported MOFs. These remarkable features illustrate that ZIF-derived nitrogen-doped porous carbon is an excellent adsorbent for Xe adsorption and separation at room temperature.

  6. ZIF-Derived Nitrogen-Doped Porous Carbons for Xe Adsorption and Separation.

    Science.gov (United States)

    Zhong, Shan; Wang, Qian; Cao, Dapeng

    2016-01-01

    Currently, finding high capacity adsorbents with large selectivity to capture Xe is still a great challenge. In this work, nitrogen-doped porous carbons were prepared by programmable temperature carbonization of zeolitic imidazolate framework-8 (ZIF-8) and ZIF-8/xylitol composite precursors and the resultant samples are marked as Carbon-Z and Carbon-ZX, respectively. Further adsorption measurements indicate that ZIF-derived nitrogen-doped Carbon-ZX exhibits extremely high Xe capacity of 4.42 mmol g(-1) at 298 K and 1 bar, which is higher than almost all other pristine MOFs such as CuBTC, Ni/DOBDC, MOF-5 and Al-MIL-53, and even more than three times of the matrix ZIF-8 at similar conditions. Moreover, Carbon-ZX also shows the highest Xe/N2 selectivity about ~120, which is much larger than all other reported MOFs. These remarkable features illustrate that ZIF-derived nitrogen-doped porous carbon is an excellent adsorbent for Xe adsorption and separation at room temperature. PMID:26883471

  7. Metal-Organic Frameworks: Building Block Design Strategies for the Synthesis of MOFs.

    KAUST Repository

    Luebke, Ryan

    2014-09-01

    A significant and ongoing challenge in materials chemistry and furthermore solid state chemistry is to design materials with the desired properties and characteristics. The field of Metal-Organic Frameworks (MOFs) offers several strategies to address this challenge and has proven fruitful at allowing some degree of control over the resultant materials synthesized. Several methodologies for synthesis of MOFs have been developed which rely on use of predetermined building blocks. The work presented herein is focused on the utilization of two of these design principles, namely the use of molecular building blocks (MBBs) and supermolecular building blocks (SBBs) to target MOF materials having desired connectivities (topologies). These design strategies also permit the introduction of specific chemical moieties, allowing for modification of the MOFs properties. This research is predominantly focused on two platforms (rht-MOFs and ftw-MOFs) which topologically speaking are edge transitive binodal nets; ftw being a (4,12)-connected net and rht being a (3,24)-connected net. These highly connected nets (at least one node having connectivity greater than eight) have been purposefully targeted to increase the predictability of structural outcome. A general trend in topology is that there is an inverse relationship between the connectivity of the node(s) and the number of topological outcomes. Therefore the key to this research (and to effective use of the SBB and MBB approaches) is identification of conditions which allow for reliable formation of the targeted MBBs and SBBs. In the case of the research presented herein: a 12-connected Group IV or Rare Earth based hexanuclear MBB and a 24-connected transition metal based SBB were successfully targeted and synthesized. These two synthetic platforms will be presented and used as examples of how these design methods have been (and can be further) utilized to modify existing materials or develop new materials for gas storage and

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

    KAUST Repository

    Spanopoulos, Ioannis

    2015-12-22

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

  9. A cationic copper(I) iodide cluster MOF exhibiting unusual ligand assisted thermochromism.

    Science.gov (United States)

    Yadav, Ashok; Srivastava, Anant Kumar; Balamurugan, Ayyakkalai; Boomishankar, Ramamoorthy

    2014-06-14

    By employing a tridentate thiophosphoramide ligand, [(NHAQ)3P[double bond, length as m-dash]S] (AQ = 3-quinolinyl), a cationic MOF, {[Cu6I5(L(1))2](OH)·3DMF·2.5MeOH}n, was synthesized. Photo-physical studies on the 2D-MOF showed an unusual thermochromic behaviour emitting a blue fluorescence at 298 K due to the AQ chromophore and an orange-yellow phosphorescence at 77 K due to the [Cu6I5](+) unit. PMID:24760039

  10. The unique rht-MOF platform, ideal for pinpointing the functionalization and CO 2 adsorption relationship

    KAUST Repository

    Luebke, Ryan

    2012-01-01

    The uniqueness of the rht-MOF platform, based on the singular (3,24)-connected net, allows for the facile design and synthesis of functionalized materials for desired applications. Here we designed a nitrogen-rich trefoil hexacarboxylate (trigonal tri-isophthalate) ligand, which serves to act as the trigonal molecular building block while concurrently coding the formation of the targeted truncated cuboctahedral supermolecular building block (in situ), and enhancing the CO 2 uptake in the resultant rht-MOF. © 2012 The Royal Society of Chemistry.

  11. Growth of 2D sheets of a MOF on graphene surfaces to yield composites with novel gas adsorption characteristics.

    Science.gov (United States)

    Kumar, Ram; Jayaramulu, Kolleboyina; Maji, Tapas Kumar; Rao, C N R

    2014-05-28

    Homogeneous graphene-MOF composites based on a 2D pillared-bilayer MOF (Cd-PBM), {[Cd4(azpy)2(pyrdc)4(H2O)2]·9H2O}n (azpy = 4,4'-azopyridine, pyrdc = pyridine-2,3-dicarboxylate), have been synthesized, using both graphene oxide (GO) and benzoic acid functionalized graphene (BFG). The composites GO@Cd-PBM and BFG@Cd-PBM demonstrate growth of the 2D nano-sheets of MOF on the graphene surface. While the pristine MOF, Cd-PBM shows selective CO2 uptake with a single-step type-I adsorption profile, the composites show stepwise CO2 uptake with a large hysteresis. With H2O and MeOH, on the other hand, the composites show a single-step adsorption unlike the parent MOF.

  12. Highly porous ionic rht metal-organic framework for H2 and CO2 storage and separation: A molecular simulation study

    KAUST Repository

    Babarao, Ravichandar

    2010-07-06

    The storage and separation of H2 and CO2 are investigated in a highly porous ionic rht metal-organic framework (rht-MOF) using molecular simulation. The rht-MOF possesses a cationic framework and charge-balancing extraframework NO3 - ions. Three types of unique open cages exist in the framework: rhombicuboctahedral, tetrahedral, and cuboctahedral cages. The NO3 - ions exhibit small mobility and are located at the windows connecting the tetrahedral and cuboctahedral cages. At low pressures, H2 adsorption occurs near the NO 3 - ions that act as preferential sites. With increasing pressure, H2 molecules occupy the tetrahedral and cuboctahedral cages and the intersection regions. The predicted isotherm of H2 at 77 K agrees well with the experimental data. The H2 capacity is estimated to be 2.4 wt % at 1 bar and 6.2 wt % at 50 bar, among the highest in reported MOFs. In a four-component mixture (15:75:5:5 CO2/H 2/CO/CH4) representing a typical effluent gas of H 2 production, the selectivity of CO2/H2 in rht-MOF decreases slightly with increasing pressure, then increases because of cooperative interactions, and finally decreases as a consequence of entropy effect. By comparing three ionic MOFs (rht-MOF, soc-MOF, and rho-ZMOF), we find that the selectivity increases with increasing charge density or decreasing free volume. In the presence of a trace amount of H2O, the interactions between CO2 and NO3 - ions are significantly shielded by H2O; consequently, the selectivity of CO 2/H2 decreases substantially. © 2010 American Chemical Society.

  13. Visualizing MOF Mixed Matrix Membranes at the Nanoscale: Towards Structure-Performance Relationships in CO 2 /CH 4 Separation Over NH 2 -MIL-53(Al)@PI

    NARCIS (Netherlands)

    Rodenas, T.; Van Dalen, M.; Garcia-Perez, E.; Serra-Crespo, P.; Zornoza, B.; Kapteijn, F.; Gascon, J.

    2013-01-01

    Mixed matrix membranes (MMMs) composed of metal organic framework (MOF) fi llers embedded in a polymeric matrix represent a promising alternative for CO 2 removal from natural gas and biogas. Here, MMMs based on NH 2 -MIL-53(Al) MOF and polyimide are successfully synthesized with MOF loadings up to

  14. Post-assembly transformations of porphyrin-containing metal-organic framework (MOF) films fabricated via automated layer-by-layer coordination

    KAUST Repository

    So, Monica

    2015-01-01

    Herein, we demonstrate the robustness of layer-by-layer (LbL)-assembled, pillared-paddlewheel-type MOF films toward conversion to new or modified MOFs via solvent-assisted linker exchange (SALE) and post-assembly linker metalation. Further, we show that LbL synthesis can afford MOFs that have proven inaccessible through other de novo strategies.

  15. Diffusion-Controlled Rotation of Triptycene in a Metal–Organic Framework (MOF) Sheds Light on the Viscosity of MOF-Confined Solvent

    Science.gov (United States)

    2016-01-01

    Artificial molecular machines are expected to operate under conditions of very low Reynolds numbers with inertial forces orders of magnitude smaller than viscous forces. While these conditions are relatively well understood in bulk fluids, opportunities to assess the role of viscous forces in confined crystalline media are rare. Here we report one such example of diffusion-controlled rotation in crystals and its application as a probe for viscosity of MOF-confined solvent. We describe the preparation and characterization of three pillared paddlewheel MOFs, with 9,10-bis(4-pyridylethynyl)triptycene 3 as a pillar and molecular rotator, and three axially substituted dicarboxylate linkers with different lengths and steric bulk. The noncatenated structure with a bulky dicarboxylate linker (UCLA-R3) features a cavity filled by 10 molecules of N,N-dimethylformamide (DMF). Solid-state 2H NMR analysis performed between 293 and 343 K revealed a fast 3-fold rotation of the pillar triptycene group with the temperature dependence consistent with a site exchange process determined by rotator-solvent interactions. The dynamic viscosity of the MOF-confined solvent was estimated to be 13.3 N·s/m2 (or Pa·s), which is 4 orders of magnitude greater than that of bulk DMF (8.2 × 10–4 N·s/m2), and comparable to that of honey. PMID:27725958

  16. Pentiptycene-Based Luminescent Cu (II) MOF Exhibiting Selective Gas Adsorption and Unprecedentedly High-Sensitivity Detection of Nitroaromatic Compounds (NACs)

    Science.gov (United States)

    Zhang, Minghui; Zhang, Liangliang; Xiao, Zhenyu; Zhang, Qinhui; Wang, Rongming; Dai, Fangna; Sun, Daofeng

    2016-02-01

    The assembly of a fluorescent pentiptycene-based ligand with copper ion resulted in the formation of a 3D porous metal-organic framework (UPC-21) based on well-known paddlewheel SBUs. UPC-21 exhibits selective adsorption of CO2 over CH4 and N2 at 273 K and 295 K, C2H2 over CH4 at 273 K. The most significant performance of UPC-21 is its highly efficient detection of NACs such as 4-NP, 1,4-DNB, NB, and 1,3-DNB with the calculated quenching constants, Ksv, being 3.097 × 106, 1.406 × 106, 4.420 × 105, and 1.498 × 105 M-1 for 4-NP, 1,4-DNB, NB, 1,3-DNB, respectively, which keeps a record on the fluorescence detection of NACs. This is the first porous Cu(II) MOF that exhibits fluorescent detection of NACs with high sensitivities.

  17. 金属骨架有机多孔碳的制备及其在锂空气电池中的应用∗%Preparation of Porous Carbon Based on Metal Organic Framework and Its Application for Lithium-Air Battery

    Institute of Scientific and Technical Information of China (English)

    王先友; 宋云峰; 白艳松; 江兰兰; 舒洪波; 杨秀康; 王灏; 赵青蓝; 易兰花

    2014-01-01

    A metal organic framework porous carbon (MOF-PC)has been prepared by terephthalic acid-zinc complex (MOF-5)and employed in lithium oxygen batteries for the first time.The physical and elec-trochemical properties of the as-prepared carbon sample are investigated by powder X-ray diffraction (XRD),scanning electron microscopy (SEM),transmission electron microscopy (TEM),N2 adsorption-desorption isotherm and galvanostatic charge/discharge.The results show that the as-prepared MOF-PC is amorphous structure with a specific surface area of 654 m2 ·g-1 .The lithium oxygen battery using the MOF-PC carbon black as air electrode shows a higher capacity of 3 183 mAh·g-1 at a current density of 0.1 mA·cm-2 ,it increased about 90% capacity compared to traditional Super P carbon black.%以苯二甲酸-锌配位化合物(MOF-5)为原料合成金属骨架有机多孔碳MOF-PC,并首次应用于锂空气电池.采用XRD、SEM、TEM、氮气脱吸附和恒流充放电测试研究了MOF-PC的物理及电化学性能.结果表明,样品MOF-PC为无定型碳,比表面积为654 m2·g-1.以MOF-PC为空气电极的锂空气电池在0.1 mA·cm-2电流密度下放电比容量高达3183 mAh·g-1,比传统碳材料(Super P)在相同电流密度下的容量高90%.

  18. Adsorption isotherms and selectivity of CO/N2/CO2 on MOF-74(Ni)%CO/N2/CO2在MOF-74(Ni)上吸附相平衡和选择性

    Institute of Scientific and Technical Information of China (English)

    刘有毅; 黄艳; 何嘉杰; 肖静; 夏启斌; 李忠

    2015-01-01

    This work investigates the adsorption performance of adsorbent MOF-74(Ni) for CO/N2 and CO2/CO2 binary gas mixtures. Adsorbent MOF-74(Ni) with high density of coordinatively unsaturated sites was synthesized by a hydrothermal method, and characterized with N2 adsorption, P-XRD, and SEM. The adsorption isotherms of CO, N2 and CO2 on MOF-74(Ni) were measured, and the selectivities for CO/N2 and CO/CO2 were calculated based on ideal adsorbed solution theory (IAST). Results showed that adsorbent MOF-74(Ni) achieved superior CO adsorption capacity of 6.15 mmol·g−1 at 298 K and 0.1 MPa, and as low as 0.86 mmol·g−1 for N2. In low pressure range of 0—40 kPa, MOF-74(Ni) showed significantly higher uptake for CO than that for CO2. Moreover, IAST-predicted CO/N2 selectivity of MOF-74(Ni) is above 1000, and its CO/CO2 selectivity is in the range of 4—9. It suggests that MOF-74(Ni) is more favorable for CO adsorption than N2and CO2 adsorption.%主要研究了MOF-74(Ni)材料对CO/N2/CO2的吸附分离性能。应用水热法合成制备MOF-74(Ni),分别采用全自动表面积吸附仪、P-XRD、扫描电子显微镜对材料的孔隙结构和晶体形貌进行了表征,应用静态吸附法测定了CO、N2和CO2在MOF-74(Ni)上的吸附等温线,应用DSLF方程模拟了3种气体MOF-74(Ni)上的吸附等温线,依据IAST理论模型计算了MOF-74(Ni)对CO/N2二元混合物和CO/CO2二元混合物的吸附选择性。研究结果表明:在0.1 MPa和常温条件下,MOF-74(Ni)材料对CO吸附容量高达6.15 mmol·g−1,而相同条件下N2的吸附量只有0.86 mmol·g−1。MOF-74(Ni)在低压下(0~40 kPa)对CO的吸附量明显高于其对CO2的吸附量。应用IAST模型估算MOF-74(Ni)对二元混合物吸附选择性的结果表明:MOF-74(Ni)对CO/N2混合物的吸附选择性在1000以上;MOF-74(Ni)对 CO/CO2的吸附选择性在4~9范围,在所研究的二元气体混合物吸附体系中,MOF-74(Ni)都能优先吸附CO。

  19. Turn-on fluorescence triggered by selective internal dye replacement in MOFs.

    Science.gov (United States)

    Wuttke, Stefan; Dietl, Christian; Hinterholzinger, Florian M; Hintz, Henrik; Langhals, Heinz; Bein, Thomas

    2014-04-01

    Coordinatively unsaturated metal sites (CUS) are used to create dye-functionalized metal-organic frameworks (MOFs). The quenching of dye fluorescence through interactions with the CUS can be utilised for chemical sensing of Lewis bases that displace the dye from the CUS, resulting in a triggered turn-on fluorescence signal.

  20. Ethene/ethane separation by the MOF membrane ZIF-8: Molecular correlation of permeation, adsorption, diffusion

    NARCIS (Netherlands)

    H. Bux; C. Chmelik; R. Krishna; J. Caro

    2011-01-01

    The newly developed MOF membrane ZIF-8 separates an equimolar ethene/ethane mixture at room temperature for 1 and 6 bar feed pressure, respectively, with a selectivity of 2.8 and 2.4. Independent sorption uptake studies of an ethene/ethane mixture on a big ZIF-8 single crystal by IR microscopy detec

  1. Chemistry in confined spaces: Reactivity of the Zn-MOF-74 channels

    CERN Document Server

    Zuluaga, S; Tan, K; Arter, C A; Li, J; Chabal, I J; Thonhauser, T

    2016-01-01

    Using infrared spectroscopy combined with ab initio methods we study reactions of H$_2$O and CO inside the confined spaces of Zn-MOF-74 channels. Our results show that, once the water dissociation reaction H$_2$O$\\;\\rightarrow\\;$OH+H takes place at the metal centers, the addition of 40 Torr of CO at 200 $^{\\circ}$C starts the production of formic acid via OH+H+CO$\\;\\rightarrow\\;$HCO$_2$H. Our detailed analysis shows that the overall reaction H$_2$O+CO$\\;\\rightarrow\\;$HCO$_2$H takes place in the confinement of MOF-74 without an external catalyst, unlike the same reaction on flat surfaces. This discovery has several important consequences: It opens the door to a new set of catalytic reactions inside the channels of the MOF-74 system, it suggests that a recovery of the MOF's adsorption capacity is possible after it has been exposed to water (which in turn stabilizes its crystal structure), and it produces the important industrial feedstock formic acid.

  2. Surface-modified CAU-10 MOF materials as humidity sensors: impedance spectroscopic study on water uptake.

    Science.gov (United States)

    Weiss, Alexander; Reimer, Nele; Stock, Norbert; Tiemann, Michael; Wagner, Thorsten

    2015-09-01

    Metal-organic frameworks (MOFs) are crystalline microporous materials with tunable chemical and physical properties. By combining various metal clusters with different interconnecting organic linkers, the pore structure, crystallinity, as well as the surface properties can be modified. In the present work, modification of the organic linker molecules is utilized to synthesize CAU-10 type MOFs with variable affinity of the pore surface to water. In principle, this should influence the accessibility of the pores for water vapor and therefore offer a tool to control its sorption properties. For a deeper understanding we studied the water sorption characteristics and compared the results to the conductive and dielectric properties studied by impedance spectroscopy. Spectra in a wide frequency range from 1 mHz to 1 MHz were recorded. Data analysis is performed using the Havriliak-Negami model. The MOFs are also tested as sensitive layers for capacitive humidity sensing by correlating the change in permittivity of the materials with the amount of physisorbed water. Such an MOF-based sensor was tested with respect to environmental monitoring and compared to a commonly used commercial humidity sensor. PMID:26227316

  3. Metal organic framework synthesis in the presence of surfactants: towards hierarchical MOFs?

    NARCIS (Netherlands)

    Seoane, B.; Dikhtiarenko, A.; Mayoral, A.; Tellez, C.; Coronas,J.; Kapteijn, F.; Gascon, J.

    2015-01-01

    The effect of synthesis pH and H2O/EtOH molar ratio on the textural properties of different aluminium trimesate metal organic frameworks (MOFs) prepared in the presence of the well-known cationic surfactant cetyltrimethylammonium bromide (CTAB) at 120 °C was studied with the purpose of obtaining a M

  4. Iodine confinement into metal-organic frameworks (MOFs)-low temperature sintering glasses to form novel glass composite material (GCM) alternative waste forms.

    Energy Technology Data Exchange (ETDEWEB)

    Nenoff, Tina Maria; Garino, Terry J.; Sava, Dorina Florentina

    2010-11-01

    The safe handling of reprocessed fuel addresses several scientific goals, especially when considering the capture and long-term storage of volatile radionuclides that are necessary during this process. Despite not being a major component of the off-gas, radioiodine (I{sub 2}) is particularly challenging, because it is a highly mobile gas and {sup 129}I is a long-lived radionuclide (1.57 x 10{sup 7} years). Therefore, its capture and sequestration is of great interest on a societal level. Herein, we explore novel routes toward the effective capture and storage of iodine. In particular, we report on the novel use of a new class of porous solid-state functional materials (metal-organic frameworks, MOFs), as high-capacity adsorbents of molecular iodine. We further describe the formation of novel glass-composite material (GCM) waste forms from the mixing and sintering of the I{sub 2}-containing MOFs with Bi-Zn-O low-temperature sintering glasses and silver metal flakes. Our findings indicate that, upon sintering, a uniform monolith is formed, with no evidence of iodine loss; iodine is sequestered during the heating process by the in situ formation of AgI. Detailed materials characterization analysis is presented for the GCMs. This includes powder X-ray diffraction, scanning electron microscopy coupled with energy-dispersive spectroscopy (SEM-EDS), thermal analysis (thermogravimetric analysis (TGA)), and chemical durability tests including aqueous leach studies (product consistency test (PCT)), with X-ray fluorescence (XRF) and inductively coupled plasma-mass spectrometry (ICP-MS) of the PCT leachate.

  5. Iodine confinement into metal-organic frameworks (MOFs): Low temperature sintering glasses to form novel glass composite material (GCM) alternative waste forms

    International Nuclear Information System (INIS)

    The safe handling of reprocessed fuel addresses several scientific goals, especially when considering the capture and long-term storage of volatile radionuclides that are necessary during this process. Despite not being a major component of the off-gas, radioiodine (I2) is particularly challenging, because it is a highly mobile gas and 129I is a long-lived radionuclide (1.57 x 107 years). Therefore, its capture and sequestration is of great interest on a societal level. Herein, we explore novel routes toward the effective capture and storage of iodine. In particular, we report on the novel use of a new class of porous solid-state functional materials (metal-organic frameworks, MOFs), as high-capacity adsorbents of molecular iodine. We further describe the formation of novel glass-composite material (GCM) waste forms from the mixing and sintering of the I2-containing MOFs with Bi-Zn-O low-temperature sintering glasses and silver metal flakes. Our findings indicate that, upon sintering, a uniform monolith is formed, with no evidence of iodine loss; iodine is sequestered during the heating process by the in situ formation of AgI. Detailed materials characterization analysis is presented for the GCMs. This includes powder X-ray diffraction, scanning electron microscopy coupled with energy-dispersive spectroscopy (SEM-EDS), thermal analysis (thermogravimetric analysis (TGA)), and chemical durability tests including aqueous leach studies (product consistency test (PCT)), with X-ray fluorescence (XRF) and inductively coupled plasma-mass spectrometry (ICP-MS) of the PCT leachate.

  6. MOF catalysis of Fe(II)-to-Fe(III) reaction for an ultrafast and one-step generation of the Fe2O3@MOF composite and uranium(vi) reduction by iron(ii) under ambient conditions.

    Science.gov (United States)

    Xiong, Yang Yang; Li, Jian Qiang; Yan, Chang Sheng; Gao, Heng Ya; Zhou, Jian Ping; Gong, Le Le; Luo, Ming Biao; Zhang, Le; Meng, Pan Pan; Luo, Feng

    2016-08-01

    Herein, we demonstrate that Zn-MOF-74 enables the ultrafast and one-step generation of the Fe2O3@MOF composite once Zn-MOF-74 contacts with FeSO4 solution. This unique reaction can be further applied in catalysis of U(vi) reduction by Fe(ii) under ambient conditions. The results provide a highly renovated strategy for U(vi) reduction by Fe(ii) just under ambient conditions, which completely subvert all established methods about U(vi) reduction by Fe(ii) in which O2- and CO2-free conditions are absolutely required. PMID:27380820

  7. Luminescent properties of metal-organic framework MOF-5: relativistic time-dependent density functional theory investigations.

    Science.gov (United States)

    Ji, Min; Lan, Xin; Han, Zhenping; Hao, Ce; Qiu, Jieshan

    2012-11-19

    The electronically excited state and luminescence property of metal-organic framework MOF-5 were investigated using relativistic density functional theory (DFT) and time-dependent DFT (TDDFT). The geometry, IR spectra, and UV-vis spectra of MOF-5 in the ground state were calculated using relativistic DFT, leading to good agreement between the experimental and theoretical results. The frontier molecular orbitals and electronic configuration indicated that the luminescence mechanism in MOF-5 follows ligand-to-ligand charge transfer (LLCT), namely, π* → π, rather than emission with the ZnO quantum dot (QD) proposed by Bordiga et al. The geometry and IR spectra of MOF-5 in the electronically excited state have been calculated using the relativistic TDDFT and compared with those for the ground state. The comparison reveals that the Zn4O13 QD is rigid, whereas the ligands BDC(2-) are nonrigid. In addition, the calculated emission band of MOF-5 is in good agreement with the experimental result and is similar to that of the ligand H2BDC. The combined results confirmed that the luminescence mechanism for MOF-5 should be LLCT with little mixing of the ligand-to-metal charge transfer. The reason for the MOF-5 luminescence is explained by the excellent coplanarity between the six-membered ring consisting of zinc, oxygen, carbon, and the benzene ring. PMID:23136957

  8. Porous metal-organic frameworks for heterogeneous biomimetic catalysis.

    Science.gov (United States)

    Zhao, Min; Ou, Sha; Wu, Chuan-De

    2014-04-15

    Metalloporphyrins are the active sites in monooxygenases that oxidize a variety of substrates efficiently and under mild conditions. Researchers have developed artificial metalloporphyrins, but these structures have had limited catalytic applications. Homogeneous artificial metalloporphyrins can undergo catalytic deactivation via suicidal self-oxidation, which lowers their catalytic activity and sustainability relative to their counterparts in Nature. Heme molecules in protein scaffolds can maintain high efficiency over numerous catalytic cycles. Therefore, we wondered if immobilizing metalloporphyrin moieties within porous metal-organic frameworks (MOFs) could stabilize these structures and facilitate the molecular recognition of substrates and produce highly efficient biomimetic catalysis. In this Account, we describe our research to develop multifunctional porphyrinic frameworks as highly efficient heterogeneous biomimetic catalysts. Our studies indicate that porous porphyrinic frameworks provide an excellent platform for mimicking the activity of biocatalysts and developing new heterogeneous catalysts that effect new chemical transformations under mild conditions. The porous structures and framework topologies of the porphyrinic frameworks depend on the configurations, coordination donors, and porphyrin metal ions of the metalloporphyrin moieties. To improve the activity of porous porphyrinic frameworks, we have developed a two-step synthesis that introduces the functional polyoxometalates (POMs) into POM-porphyrin hybrid materials. To tune the pore structures and the catalytic properties of porphyrinic frameworks, we have designed metalloporphyrin M-H8OCPP ligands with four m-benzenedicarboxylate moieties, and introduced the secondary auxiliary ligands. The porphyrin metal ions and the secondary functional moieties that are incorporated into porous metal-organic frameworks greatly influence the catalytic properties and activities of porphyrinic frameworks in

  9. 3D hybrid-porous carbon derived from carbonization of metal organic frameworks for high performance supercapacitors

    Science.gov (United States)

    Bao, Weizhai; Mondal, Anjon Kumar; Xu, Jing; Wang, Chengyin; Su, Dawei; Wang, Guoxiu

    2016-09-01

    We report a rational design and synthesis of 3D hybrid-porous carbon with a hierarchical pore architecture for high performance supercapacitors. It contains micropores (<2 nm diameter) and mesopores (2-4 nm), derived from carbonization of unique porous metal organic frameworks (MOFs). Owning to the synergistic effect of micropores and mesopores, the hybrid-porous carbon has exceptionally high ion-accessible surface area and low ion diffusion resistance, which is desired for supercapacitor applications. When applied as electrode materials in supercapacitors, 3D hybrid-porous carbon demonstrates a specific capacitance of 332 F g-1 at a constant charge/discharge current of 500 mA g-1. The supercapacitors can endure more than 10,000 cycles without degradation of capacitance.

  10. Sex-biased transcription enhancement by a 5' tethered Gal4-MOF histone acetyltransferase fusion protein in Drosophila

    Directory of Open Access Journals (Sweden)

    Belikoff Esther J

    2010-11-01

    Full Text Available Abstract Background In male Drosophila melanogaster, the male specific lethal (MSL complex is somehow responsible for a two-fold increase in transcription of most X-linked genes, which are enriched for histone H4 acetylated at lysine 16 (H4K16ac. This acetylation requires MOF, a histone acetyltransferase that is a component of the MSL complex. MOF also associates with the non-specific lethal or NSL complex. The MSL complex is bound within active genes on the male X chromosome with a 3' bias. In contrast, the NSL complex is enriched at promoter regions of many autosomal and X-linked genes in both sexes. In this study we have investigated the role of MOF as a transcriptional activator. Results MOF was fused to the DNA binding domain of Gal4 and targeted to the promoter region of UAS-reporter genes in Drosophila. We found that expression of a UAS-red fluorescent protein (DsRed reporter gene was strongly induced by Gal4-MOF. However, DsRed RNA levels were about seven times higher in female than male larvae. Immunostaining of polytene chromosomes showed that Gal4-MOF co-localized with MSL1 to many sites on the X chromosome in male but not female nuclei. However, in female nuclei that express MSL2, Gal4-MOF co-localized with MSL1 to many sites on polytene chromosomes but DsRed expression was reduced. Mutation of conserved active site residues in MOF (Glu714 and Cys680 reduced HAT activity in vitro and UAS-DsRed activation in Drosophila. In the presence of Gal4-MOF, H4K16ac levels were enriched over UAS-lacZ and UAS-arm-lacZ reporter genes. The latter utilizes the constitutive promoter from the arm gene to drive lacZ expression. In contrast to the strong induction of UAS-DsRed expression, UAS-arm-lacZ expression increased by about 2-fold in both sexes. Conclusions Targeting MOF to reporter genes led to transcription enhancement and acetylation of histone H4 at lysine 16. Histone acetyltransferase activity was required for the full transcriptional

  11. Synthesis and Characterization of Metal-Organic Frameworks (MOFs) for Photon Collection and Energy Transfer

    Science.gov (United States)

    So, Monica C.

    . To address problem (a), we incorporated antenna molecules (i.e. perylene diimides) to expand light collection and then transfer energy to the primary chromophores. To address problem (b), we observed that excitons can achieve up to 2,025 hops in a porphyrin-based metal-organic framework (MOF) single crystal within its 3 ns lifetime. By precisely aligning the chromophores in the MOF, we showed that long-distance exciton transport (i.e. ultra-fast, sequential hopping) was consistent with the well-established Forster theory. To address problems (c) and (d), we introduced MOF components one step at a time to optimize optical path length and crystal-thickness. This allowed us to incorporate MOFs (normally bulk crystals) into a MOF film. The approach exploited both MOF chemistry and layer-by-layer (LbL) assembly of crystalline MOFs in a highly controlled fashion on functional surfaces. We also incorporated good light-harvesting molecules as struts in MOFs to increase the visible absorption. Designing MOF-based OPVs can provide insight into solar energy conversion. This can potentially lead to much higher efficiencies, based on the simultaneous resolution of the four challenges hindering OPV performance.

  12. Amine Functionalized Porous Network

    KAUST Repository

    Eddaoudi, Mohamed

    2015-05-28

    Amine groups can be introduced in porous materials by a direct (one pot) or post-synthetic modification (PSM) process on aldehyde groups, and the resulting porous materials have increased gas affinity.

  13. Multi-Column Experimental Test Bed Using CaSDB MOF for Xe/Kr Separation

    Energy Technology Data Exchange (ETDEWEB)

    Welty, Amy Keil [Idaho National Lab. (INL), Idaho Falls, ID (United States); Greenhalgh, Mitchell Randy [Idaho National Lab. (INL), Idaho Falls, ID (United States); Garn, Troy Gerry [Idaho National Lab. (INL), Idaho Falls, ID (United States)

    2016-03-01

    Processing of spent nuclear fuel produces off-gas from which several volatile radioactive components must be separated for further treatment or storage. As part of the Off-gas Sigma Team, parallel research at INL and PNNL has produced several promising sorbents for the selective capture of xenon and krypton from these off-gas streams. In order to design full-scale treatment systems, sorbents that are promising on a laboratory scale must be proven under process conditions to be considered for pilot and then full-scale use. To that end, a bench-scale multi-column system with capability to test multiple sorbents was designed and constructed at INL. This report details bench-scale testing of CaSDB MOF, produced at PNNL, and compares the results to those reported last year using INL engineered sorbents. Two multi-column tests were performed with the CaSDB MOF installed in the first column, followed with HZ-PAN installed in the second column. The CaSDB MOF column was placed in a Stirling cryocooler while the cryostat was employed for the HZ-PAN column. Test temperatures of 253 K and 191 K were selected for the first column while the second column was held at 191 K for both tests. Calibrated volume sample bombs were utilized for gas stream analyses. At the conclusion of each test, samples were collected from each column and analyzed for gas composition. While CaSDB MOF does appear to have good capacity for Xe, the short time to initial breakthrough would make design of a continuous adsorption/desorption cycle difficult, requiring either very large columns or a large number of smaller columns. Because of the tenacity with which Xe and Kr adhere to the material once adsorbed, this CaSDB MOF may be more suitable for use as a long-term storage solution. Further testing is recommended to determine if CaSDB MOF is suitable for this purpose.

  14. Direct white-light and a dual-channel barcode module from Pr(III)-MOF crystals.

    Science.gov (United States)

    Du, Bin-Bin; Zhu, Yi-Xuan; Pan, Mei; Yue, Mei-Qin; Hou, Ya-Jun; Wu, Kai; Zhang, Lu-Yin; Chen, Ling; Yin, Shao-Yun; Fan, Ya-Nan; Su, Cheng-Yong

    2015-08-14

    Direct white-light emission and further a dual-channel readable barcode module in both visible and NIR region was established by single-component homo-metallic Pr(iii)-MOF crystals for the first time. PMID:26152399

  15. Prediction of adsorption of small molecules in porous materials based on ab initio force field method

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Computational prediction of adsorption of small molecules in porous materials has great impact on the basic and applied research in chemical engineering and material sciences. In this work,we report an approach based on grand canonical ensemble Monte Carlo(GCMC) simulations and ab initio force fields. We calculated the adsorption curves of ammonia in ZSM-5 zeolite and hydrogen in MOF-5(a metal-organic-framework material). The predictions agree well with experimental data. Because the predictions are based on the first principle force fields,this approach can be used for the adsorption prediction of new molecules or materials without experimental data as guidance.

  16. Highly monodisperse M III-based soc -MOFs (M = in and Ga) with cubic and truncated cubic morphologies

    KAUST Repository

    Pang, Maolin

    2012-08-15

    In this work, we carry out an investigation on shape-controlled growth of In III- and Ga III-based square-octahedral metal-organic frameworks (soc-MOFs). In particular, controllable crystal morphological evolution from simple cubes to complex octadecahedra has been achieved, and resultant highly uniform crystal building blocks promise new research opportunities for preparation of self-assembled MOF materials and related applications. © 2012 American Chemical Society.

  17. Systematic modulation and enhancement of CO{sub 2} : N{sub 2} selectivity and water stability in an isoreticular series of bio-MOF-11 analogues

    Energy Technology Data Exchange (ETDEWEB)

    Li, Tao; Chen, De-Li; Sullivan, Jeanne E.; Kozlowski, Mark T.; Johnson, J Karl; Rosi, Nathaniel L.

    2013-02-01

    An isoreticular series of cobalt-adeninate bio-MOFs (bio-MOFs 11-14) is reported. The pores of bio-MOFs 11-14 are decorated with acetate, propionate, butyrate, and valerate, respectively. The nitrogen (N{sub 2}) and carbon dioxide (CO{sub 2}) adsorption properties of these materials are studied and compared. The isosteric heats of adsorption for CO{sub 2} are calculated, and the CO{sub 2}:N{sub 2} selectivities for each material are 10 determined. As the lengths of the aliphatic chains decorating the pores in bio-MOFs 11-14 increase, the BET surface areas decrease from 1148 m{sup 2}/g to 17 m{sup 2}/g while the CO{sub 2}:N{sub 2} selectivities predicted from ideal adsorbed solution theory at 1 bar and 273 K for a 10:90 CO{sub 2}:N{sub 2} mixture range from 73:1 for bio-MOF-11 to 123:1 for bio-MOF-12 and finally to 107:1 for bio-MOF-13. At 298 K, the selectivities are 43:1 for bio-MOF-11, 52:1 for bio-MOF-12, and 40:1 for bio-MOF-13. Additionally, it is shown that 15 bio-MOF-14 exhibits a unique molecular sieving property that allows it to adsorb CO{sub 2} but not N{sub 2} at 273 and 298 K. Finally, the water stability of bio-MOFs 11-14 increases with increasing aliphatic chain length. Bio-MOF-14 exhibits no loss of crystallinity or porosity after soaking in water for one month.

  18. Therapeutic application of molecular adsorbents recirculating system in various pathogenic MODS/MOF patients

    Institute of Scientific and Technical Information of China (English)

    LUO Hong-tao; GUO Li-min; WU Min; LIU Quan-mei; WANG Min-min

    2005-01-01

    @@ Multiple organ dysfunction syndrome (MODS) or multiple organ failure (MOF) is a syndrome which is frequently related to shock and sepsis, and has been described as the most common cause of death in the noncoronary critical care unit. The potential pathogenesis of the septic and systemic inflammatory response syndrome (SIRS) response has been increasingly associated with the development and aggravation of MODS or MOF. And studies in this respect have also demonstrated that there is a higher risk of mortality associated with some specific organ systems when they are dysfunctional, thus leading to the failures of the liver, brain, lung, and kidney.1 The liver interacts with many other organ systems, and liver dysfunction may act collectively in the production of organ system dysfunction, thus finally ending up with MODS.2

  19. Tailored Porous Materials

    Energy Technology Data Exchange (ETDEWEB)

    BARTON,THOMAS J.; BULL,LUCY M.; KLEMPERER,WALTER G.; LOY,DOUGLAS A.; MCENANEY,BRIAN; MISONO,MAKOTO; MONSON,PETER A.; PEZ,GUIDO; SCHERER,GEORGE W.; VARTULI,JAMES C.; YAGHI,OMAR M.

    1999-11-09

    Tailoring of porous materials involves not only chemical synthetic techniques for tailoring microscopic properties such as pore size, pore shape, pore connectivity, and pore surface reactivity, but also materials processing techniques for tailoring the meso- and the macroscopic properties of bulk materials in the form of fibers, thin films and monoliths. These issues are addressed in the context of five specific classes of porous materials: oxide molecular sieves, porous coordination solids, porous carbons, sol-gel derived oxides, and porous heteropolyanion salts. Reviews of these specific areas are preceded by a presentation of background material and review of current theoretical approaches to adsorption phenomena. A concluding section outlines current research needs and opportunities.

  20. Encapsulation of curcumin in cyclodextrin-metal organic frameworks: Dissociation of loaded CD-MOFs enhances stability of curcumin.

    Science.gov (United States)

    Moussa, Zeinab; Hmadeh, Mohamad; Abiad, Mohamad G; Dib, Omar H; Patra, Digambara

    2016-12-01

    Curcumin has been successfully encapsulated in cyclodextrin-metal organic frameworks (CD-MOFs) without altering their crystallinity. The interaction between curcumin and CD-MOFs is strong through hydrogen bond type interaction between the OH group of cyclodextrin of CD-MOFs and the phenolic hydroxyl group of the curcumin. Interestingly, dissolving the curcumin loaded CD-MOFs crystals in water results in formation of a unique complex between curcumin, γCD and potassium cations. In fact, the initial interaction between curcumin and CD-MOF is crucial for the formation of the latter. This new complex formed in alkaline media at pH 11.5 has maximum absorbance at 520nm and emittance at 600nm. Most importantly, the stability of curcumin in this complex was enhanced by at least 3 orders of magnitude compared to free curcumin and curcumin:γ-CD at pH 11.5. These results suggest a promising benign system of CD-MOFs, which can be used to store and stabilize curcumin for food applications.

  1. Encapsulation of curcumin in cyclodextrin-metal organic frameworks: Dissociation of loaded CD-MOFs enhances stability of curcumin.

    Science.gov (United States)

    Moussa, Zeinab; Hmadeh, Mohamad; Abiad, Mohamad G; Dib, Omar H; Patra, Digambara

    2016-12-01

    Curcumin has been successfully encapsulated in cyclodextrin-metal organic frameworks (CD-MOFs) without altering their crystallinity. The interaction between curcumin and CD-MOFs is strong through hydrogen bond type interaction between the OH group of cyclodextrin of CD-MOFs and the phenolic hydroxyl group of the curcumin. Interestingly, dissolving the curcumin loaded CD-MOFs crystals in water results in formation of a unique complex between curcumin, γCD and potassium cations. In fact, the initial interaction between curcumin and CD-MOF is crucial for the formation of the latter. This new complex formed in alkaline media at pH 11.5 has maximum absorbance at 520nm and emittance at 600nm. Most importantly, the stability of curcumin in this complex was enhanced by at least 3 orders of magnitude compared to free curcumin and curcumin:γ-CD at pH 11.5. These results suggest a promising benign system of CD-MOFs, which can be used to store and stabilize curcumin for food applications. PMID:27374559

  2. Synthesis of rare earth metal-organic frameworks (Ln-MOFs) and their properties of adsorption desulfurization

    Institute of Scientific and Technical Information of China (English)

    刘想; 王景艳; 李庆远; 蒋赛; 张天浩; 季生福

    2014-01-01

    The rare earth metal-organic frameworks (Ln-MOFs) materials, Ln(BTC)(H2O)·(DMF), were synthesized using the rare earth metal (Ln=Sm, Eu, Tb, Y) and 1,3,5-trimesic acid (BTC) as a metal ion center and ligand, respectively. X-ray diffraction (XRD) and infrared spectroscopy (FT-IR) were employed to characterize the Ln-MOFs structural features. The property of adsorption desul-furization of Ln-MOFs materials was evaluated with thiophene/n-octane as model oil. The results showed that Ln-MOFs with rare earth metals Sm, Eu, Tb and Y had perfect crystalline and good adsorption desulfurization ability. Y(BTC)(H2O)·(DMF) material had a comparatively better activity for the adsorption desulfurization with desulfurization rate up to 80.7%and the sulfur adsorption ca-pacity was found 30.7 mgS/g(Y-MOFs). The Ln-MOFs materials had excellent reusability.

  3. Thermodynamically Guided Synthesis of Mixed-Linker Zr-MOFs with Enhanced Tunability.

    Science.gov (United States)

    Yuan, Shuai; Qin, Jun-Sheng; Zou, Lanfang; Chen, Ying-Pin; Wang, Xuan; Zhang, Qiang; Zhou, Hong-Cai

    2016-05-25

    Guided by thermodynamics, we have synthesized two mixed-linker zirconium-based metal-organic frameworks (Zr-MOFs), namely, PCN-133 and PCN-134. Both of them possess a layer-pillar structure, in which the connection between Zr6 clusters and primary BTB linkers form a (3,6)-connected kdg layer that is further extended into 3D frameworks by auxiliary DCDPS/TCPP linkers (BTB = benzene tribenzoate, DCDPS = 4,4'-dicarboxydiphenyl sulfone, TCPP = tetrakis(4-carboxyphenyl)porphyrin). PCN-134 demonstrates high porosity (N2 uptake of 717 cm(3)·g(-1) and BET surface area of 1946 cm(2)·g(-1)) and excellent chemical stability in aqueous solutions with pH values ranging from 0 to 13. More importantly, PCN-134 tolerates the partial absence of auxiliary linkers leading to structural defects during the assembly process while preserving its framework integrity. Furthermore, the defect density can be systematically controlled by tuning the occupancy of the auxiliary linker, which in turn affects the MOF properties. For instance, the dichromate uptake of PCN-134 is tuned by adjusting the BTB/TCPP ratios, which gives rise to an efficient dichromate absorbent when the TCPP molar ratio in linkers is set as 22%. In addition, the photocatalytic reduction of Cr(VI) in aqueous solution was also performed by PCN-134-22%TCPP which exhibits excellent catalytic activity. This work not only opens up a new synthetic route toward mixed-linker MOFs, but also provides tunable control of MOF defects and, in turn, the properties.

  4. The meaning of food (MOF): The development of a new measurement tool

    OpenAIRE

    Ogden, J; Liakopoulou, E; Antilliou, G; Gough, G.

    2012-01-01

    This paper aimed to develop a reliable measurement tool to evaluate the meanings of food that could be used in both practice and research and to examine possible gender differences. A new meaning of food questionnaire (MOF) was refined across two studies (study 1, n = 451 and study 2, n = 170). The final questionnaire consisted of 25 items and 8 reliable subscales: food and sex, emotional regulation, treat, guilt, social interaction, control over life, control over food, family. The new Meani...

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

    OpenAIRE

    Shahid, Salman

    2015-01-01

    The performance of polymeric membranes is often limited by a trade-off between membrane permeability and selectivity, the so-called Robeson upper bound. Additionally, in high pressure CO2 capture applications, excessive swelling of the polymer membrane often leads to plasticization resulting in decreased separation performances. The main goal of this work was to develop high-performance polymeric Mixed Matrix Membranes (MMMs) with Metal Organic Frameworks (MOFs) as the inorganic additive for ...

  6. Theoretical model estimation of guest diffusion in Metal-Organic Frameworks (MOFs)

    KAUST Repository

    Zheng, Bin

    2015-08-11

    Characterizing molecule diffusion in nanoporous matrices is critical to understanding the novel chemical and physical properties of metal-organic frameworks (MOFs). In this paper, we developed a theoretical model to fastly and accurately compute the diffusion rate of guest molecules in a zeolitic imidazolate framework-8 (ZIF-8). The ideal gas or equilibrium solution diffusion model was modified to contain the effect of periodical media via introducing the possibility of guests passing through the framework gate. The only input in our model is the energy barrier of guests passing through the MOF’s gate. Molecular dynamics (MD) methods were employed to gather the guest density profile, which then was used to deduce the energy barrier values. This produced reliable results that require a simulation time of 5 picoseconds, which is much shorter when using pure MD methods (in the billisecond scale) . Also, we used density functional theory (DFT) methods to obtain the energy profile of guests passing through gates, as this does not require specification of a force field for the MOF degrees of freedom. In the DFT calculation, we only considered one gate of MOFs each time; as this greatly reduced the computational cost. Based on the obtained energy barrier values we computed the diffusion rate of alkane and alcohol in ZIF-8 using our model, which was in good agreement with experimental test results and the calculation values from standard MD model. Our model shows the advantage of obtaining accurate diffusion rates for guests in MOFs for a lower computational cost and shorter calculation time. Thus, our analytic model calculation is especially attractive for high-throughput computational screening of the dynamic performance of guests in a framework.

  7. Interpenetration in coordination polymers: structural diversities toward porous functional materials

    Directory of Open Access Journals (Sweden)

    Ritesh Haldar

    2015-03-01

    Full Text Available Interpenetration is a natural phenomenon frequently encountered in porous coordination polymers (PCPs or metal-organic frameworks (MOFs. Traditionally interpenetration has been considered as a threat to permanent porosity and several strategies have been adopted to control the framework interpenetration. Recent literature reports have unveiled that interpenetration has paramount importance in several material properties particularly in storage and separation of small gas molecules. Such frameworks also show interesting structural flexibility based on shearing or movement of the nets and also reveals guest induced dynamic structural transformation for modulated specific functions. In this review, we will emphasize several interpenetration phenomena observed in coordination polymers, their intriguing structural aspects and fascinating material properties.

  8. Reticular Synthesis of a Series of HKUST-like MOFs with Carbon Dioxide Capture and Separation.

    Science.gov (United States)

    He, Hongming; Sun, Fuxing; Ma, Shengqian; Zhu, Guangshan

    2016-09-01

    We reported a series of HKUST-like MOFs based on multiple copper-containing secondary building units (SBUs). Compound 1 is constructed by two SBUs: Cu2(CO2)4 paddle-wheel SBUs and Cu2I2 dimer SBUs. Compound 2 has Cu2(CO2)4 paddle-wheel SBUs and Cu4I4 SBUs. Furthermore, compound 3 possesses Cu2(CO2)4 paddle-wheel SBUs, Cu2I2 dimer SBUs, and Cu(CO2)4 SBUs. These compounds are promising materials for CO2 capture and separation, because they all display commendable adsorption of CO2 and high selectivity for CO2 over CH4 and N2. It is worthy to note that compound 1 exhibits the highest Brunauer-Emmett-Teller surface area (ca. 901 m(2) g(-1)) among the MOF materials based on CuxIy SBUs. In addition, compound 3 is the first case that three copper SBUs coexist in MOFs. PMID:27556744

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

    Science.gov (United States)

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

    2015-07-01

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-07-01

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

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

    Directory of Open Access Journals (Sweden)

    V.Viditha, M.Venkateswer Rao, K.Srilatha11, V.Himabindu, Anjaneyulu Yerramilli

    2013-01-01

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

  12. Role of histone acetyltransferase MOF in the pathogenesis of multiple sclerosis%组蛋白乙酰转移酶 MOF 在多发性硬化发病机制中的作用

    Institute of Scientific and Technical Information of China (English)

    关景云; 杨阳; 邱春红; 李相芝

    2016-01-01

    目的:探讨实验性自身免疫性脑脊髓炎(EAE)小鼠发病高峰期、缓解期 Treg 细胞和组蛋白乙酰转移酶MOF 表达的变化情况,以及 MOF 对 EAE 发病机制的影响。方法将20只体质量相近的6~8周龄 C57BL/6雌鼠随机分为两组,EAE 组第0天腹股沟处皮下注射200μg MOG35-55,对照组注射等量弗氏完全佐剂,两组均腹腔注射200 ng百日咳毒素,第2天腹腔注射200 ng 百日咳毒素。取 EAE 组不同发病时期和对照组小鼠的脾脏组织。Western blotting 法检测 MOF、FOXP3和 H4K16ac 蛋白的表达情况;qRT-PCR 检测脾脏组织中 MOF、FOXP3、TLRS mRNA 的表达水平;蛋白质免疫共沉淀(CoIP)法检测 MOF 与 FOXP3在脾脏组织中有无相互作用;染色质免疫共沉淀(ChIP-qPCR)法检测 MOF 的下游靶基因;在 HCT116细胞中过表达 MOF 后检测 FOXP3、TLRS 表达的变化情况。结果EAE 组脾脏中的 MOF 及 FOXP3蛋白表达水平显著高于对照组;EAE 组小鼠脾脏中 MOF、FOXP3、IL17、TLR4、TLR5、TLR6、TLR7、TLR9 mRNA 水平显著高于对照组(P <0.05);MOF 与 FOXP3在脾脏组织中结合并有相互作用;脾脏组织中,MOF 与 FOXP3、TLR3、TLR4、TLR5、TLR6、SMAD2、SMAD3和 RoRγt 启动子结合;MOF过表达后,TLR4和 FOXP3表达量增加(P <0.05)。结论MOF 通过与 FOXP3相互作用,抑制 EAE 的发生。%Objective To investigate the activities of Treg cells and the expression of MOF in the peak and remission periods of experimental allergic encephalomyelitis(EAE)mice and the impact of MOF on the pathogenesis of EAE. Methods On Day 0,twenty 6-8 week old C57BL/6 female mice of similar weight were subcutaneously injected with 200 μg MOG35-55 or complete freund’s adjuvant (CFA)and then intraperitoneally injected with 200 ng pertussis toxin. On Day 2,the above three mice were intraperitoneally injected with 200 ng pertussis toxin.The spleen tissues of the EAE

  13. An Efficient Synthesis Strategy for Metal-Organic Frameworks: Dry-Gel Synthesis of MOF-74 Framework with High Yield and Improved Performance

    Energy Technology Data Exchange (ETDEWEB)

    Das, Atanu K.; Vemuri, Venkata Rama Ses; Kutnyakov, Igor V.; McGrail, B. Peter; Motkuri, Radha K.

    2016-06-16

    Vapor-assisted drygel synthesis of MOF-74 structure, specifically NiMOF-74 from its synthetic precursors, was conducted with high yield and improved performance showing promise for gas (CO2) and water adsorption applications. Unlike conventional synthesis, which takes 72 h, this kinetic study showed that NiMOF-74 forms within 12 h under drygel conditions with similar performance characteristics and exhibits the best performance characteristics after 48 h of heating.

  14. Probing the Structure, Stability and Hydrogen Adsorption of Lithium Functionalized Isoreticular MOF-5 (Fe, Cu, Co, Ni and Zn by Density Functional Theory

    Directory of Open Access Journals (Sweden)

    Yoshiyuki Kawazoe

    2009-04-01

    Full Text Available Li adsorption on isoreticular MOFs with metal Fe, Cu, Co, Ni and Zn was studied using density function theory. Li functionalization shows a considerable structural change associated with a volume change in isoreticular MOF-5 except for the Zn metal center. Hydrogen binding energies on Li functionalized MOFs are seen to be in the range of 0.2 eV, which is the desired value for an ideal reversible storage system. This study has clearly shown that Li doping is possible only in Zn-based MOF-5, which would be better candidate to reversibly store hydrogen.

  15. Functionalized ultra-porous titania nanofiber membranes as nuclear waste separation and sequestration scaffolds for nuclear fuels recycle.

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Haiqing; Bell, Nelson S; Cipiti, Benjamin B.; Lewis, Tom Goslee,; Sava, Dorina Florentina; Nenoff, Tina Maria

    2012-09-01

    Advanced nuclear fuel cycle concept is interested in reducing separations to a simplified, one-step process if possible. This will benefit from the development of a one-step universal getter and sequestration material so as a simplified, universal waste form was proposed in this project. We have developed a technique combining a modified sol-gel chemistry and electrospinning for producing ultra-porous ceramic nanofiber membranes with controllable diameters and porous structures as the separation/sequestration materials. These ceramic nanofiber materials have been determined to have high porosity, permeability, loading capacity, and stability in extreme conditions. These porous fiber membranes were functionalized with silver nanoparticles and nanocrystal metal organic frameworks (MOFs) to introduce specific sites to capture gas species that are released during spent nuclear fuel reprocessing. Encapsulation into a durable waste form of ceramic composition was also demonstrated.

  16. Biocompatible Zr-based nanoscale MOFs coated with modified poly(ε-caprolactone) as anticancer drug carriers.

    Science.gov (United States)

    Filippousi, Maria; Turner, Stuart; Leus, Karen; Siafaka, Panoraia I; Tseligka, Eirini D; Vandichel, Matthias; Nanaki, Stavroula G; Vizirianakis, Ioannis S; Bikiaris, Dimitrios N; Van Der Voort, Pascal; Van Tendeloo, Gustaaf

    2016-07-25

    Nanoscale Zr-based metal organic frameworks (MOFs) UiO-66 and UiO-67 were studied as potential anticancer drug delivery vehicles. Two model drugs were used, hydrophobic paclitaxel and hydrophilic cisplatin, and were adsorbed onto/into the nano MOFs (NMOFs). The drug loaded MOFs were further encapsulated inside a modified poly(ε-caprolactone) with d-α-tocopheryl polyethylene glycol succinate polymeric matrix, in the form of microparticles, in order to prepare sustained release formulations and to reduce the drug toxicity. The drugs physical state and release rate was studied at 37°C using Simulated Body Fluid. It was found that the drug release depends on the interaction between the MOFs and the drugs while the controlled release rates can be attributed to the microencapsulated formulations. The in vitro antitumor activity was assessed using HSC-3 (human oral squamous carcinoma; head and neck) and U-87 MG (human glioblastoma grade IV; astrocytoma) cancer cells. Cytotoxicity studies for both cell lines showed that the polymer coated, drug loaded MOFs exhibited better anticancer activity compared to free paclitaxel and cisplatin solutions at different concentrations. PMID:27235556

  17. Surfactant-thermal method to synthesize a new Zn(II)-trimesic MOF with confined Ru(bpy)32+ complex

    International Nuclear Information System (INIS)

    A surfactant-thermal method was used to prepare a new zinc-1,3,5-benzentricarboxylate-based metal-organic framework (ZJU-100) with confined Ru(bpy)32+ (RuBpy) complex by using surfactant PEG 400 as reaction medium. The RuBpy molecules were encapsulated between the 2-D sheets in ZJU-100. ZJU-100 showed bathochromic shift in the steady-state emission spectrum and increased emission lifetimes relative to RuBpy molecules. The extended lifetime is attributed to the reduced nonradiative decay rate due to the stabilization of RuBpy within the rigid MOF framework. These results represent the first example of MOF with confined complex synthesized by surfactant, indicating that the surfactant-thermal method could offer exciting opportunities for preparing new MOFs host/guest materials with novel structures and interesting luminescent properties. - Graphical abstract: A surfactant-thermal method was used to prepare a new zinc-1,3,5-benzentricarboxylate-based metal-organic framework (ZJU-100) with confined Ru(bpy)32+ (RuBpy) complex by using surfactant PEG 400 as reaction medium. - Highlights: • Surfactant-thermal synthesis of crystalline metal-organic framework host/guest materials. • RuBpy molecules were encapsulated between the 2-D sheets of MOFs. • Extended lifetime is observed due to the stabilization of RuBpy within the rigid MOF framework

  18. Tunable Rare Earth fcu-MOF Platform: Access to Adsorption Kinetics Driven Gas/Vapor Separations via Pore Size Contraction.

    Science.gov (United States)

    Xue, Dong-Xu; Belmabkhout, Youssef; Shekhah, Osama; Jiang, Hao; Adil, Karim; Cairns, Amy J; Eddaoudi, Mohamed

    2015-04-22

    Reticular chemistry approach was successfully employed to deliberately construct new rare-earth (RE, i.e., Eu(3+), Tb(3+), and Y(3+)) fcu metal-organic frameworks (MOFs) with restricted window apertures. Controlled and selective access to the resultant contracted fcu-MOF pores permits the achievement of the requisite sorbate cutoff, ideal for selective adsorption kinetics based separation and/or molecular sieving of gases and vapors. Predetermined reaction conditions that permitted the formation in situ of the 12-connected RE hexanuclear molecular building block (MBB) and the establishment of the first RE-fcu-MOF platform, especially in the presence of 2-fluorobenzoic acid (2-FBA) as a modulator and a structure directing agent, were used to synthesize isostructural RE-1,4-NDC-fcu-MOFs based on a relatively bulkier 2-connected bridging ligand, namely 1,4-naphthalenedicarboxylate (1,4-NDC). The subsequent RE-1,4-NDC-fcu-MOF structural features, contracted windows/pores and high concentration of open metal sites combined with exceptional hydrothermal and chemical stabilities, yielded notable gas/solvent separation properties, driven mostly by adsorption kinetics as exemplified in this work for n-butane/methane, butanol/methanol, and butanol/water pair systems. PMID:25825923

  19. Size- and shape-controlled synthesis of hexagonal bipyramidal crystals and hollow self-assembled Al-MOF spheres

    KAUST Repository

    Sarawade, Pradip

    2013-11-25

    We report an efficient protocol for the synthesis of monodisperse crystals of an aluminum (Al)-based metal organic framework (MOF) while obtaining excellent control over the size and shape solely by tuning of the reaction parameters without the use of a template or structure-directing agent. The size of the hexagonal crystals of the Al-MOF can be selectively varied from 100 nm to 2000 nm by simply changing the reaction time and temperature via its nucleation-growth mechanism. We also report a self-assembly phenomenon, observed for the first time in case of Al-MOF, whereby hollow spheres of Al-MOF were formed by the spontaneous organization of triangular sheet building blocks. These MOFs showed broad hysteresis loops during the CO2 capture, indicating that the adsorbed CO2 is not immediately desorbed upon decreasing the external pressure and is instead confined within the framework, which allows for the capture and subsequent selective trapping of CO2 from gaseous mixtures. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Tunable Rare Earth fcu-MOF Platform: Access to Adsorption Kinetics Driven Gas/Vapor Separations via Pore Size Contraction

    KAUST Repository

    Xue, Dong-Xu

    2015-03-31

    Reticular chemistry approach was successfully employed to deliberately construct new rare-earth (RE, i.e. Eu3+, Tb3+ and Y3+) fcu metal‒organic frameworks (MOFs) with restricted window apertures. Controlled and selective access to the resultant contracted fcu-MOF pores permits the achievement of the requisite sorbate cut-off ideal for selective adsorption kinetics separation and/or molecular sieving of gases and vapors. Predetermined reaction conditions that permitted the formation in-situ of the 12-connected RE hexanuclear molecular building block (MBB) and the establishment of the RE-fcu-MOF plat-form, especially in the presence of 2-fluorobenzoic acid (2-FBA) as a modulator and a structure directing agent, were used to synthesize isostructural RE-1,4-NDC-fcu-MOFs based on a relatively bulkier 2-connected bridging ligand, namely 1,4-naphthalenedicarboxylate (1,4-NDC). The subsequent RE-1,4-NDC-fcu-MOF structural features, contracted windows/pores and high concentration of open metal sites combined with exceptional hydrothermal and chemical stabilities, yielded nota-ble gas/solvent separation properties, driven mostly by adsorption kinetics as exemplified in this work for n-butane/methane, butanol/methanol and butanol/water pair systems.

  1. Side-chain control of porosity closure in single- and multiple-peptide-based porous materials by cooperative folding

    Science.gov (United States)

    Martí-Gastaldo, C.; Antypov, D.; Warren, J. E.; Briggs, M. E.; Chater, P. A.; Wiper, P. V.; Miller, G. J.; Khimyak, Y. Z.; Darling, G. R.; Berry, N. G.; Rosseinsky, M. J.

    2014-04-01

    Porous materials are attractive for separation and catalysis—these applications rely on selective interactions between host materials and guests. In metal-organic frameworks (MOFs), these interactions can be controlled through a flexible structural response to the presence of guests. Here we report a MOF that consists of glycyl-serine dipeptides coordinated to metal centres, and has a structure that evolves from a solvated porous state to a desolvated non-porous state as a result of ordered cooperative, displacive and conformational changes of the peptide. This behaviour is driven by hydrogen bonding that involves the side-chain hydroxyl groups of the serine. A similar cooperative closure (reminiscent of the folding of proteins) is also displayed with multipeptide solid solutions. For these, the combination of different sequences of amino acids controls the framework's response to the presence of guests in a nonlinear way. This functional control can be compared to the effect of single-point mutations in proteins, in which exchange of single amino acids can radically alter structure and function.

  2. Convection in porous media

    CERN Document Server

    Bejan, A

    2006-01-01

    Provides an introduction to convection in porous media, such as fibrous insulation, geological strata, and catalytic reactors. This third edition covers ""designed"" porous media, the theory of deformable media, modeling viscous dissipation in hyperporous media, and more. It is useful for researchers, practicing engineers and students.

  3. Hierarchical Porous Structures

    Energy Technology Data Exchange (ETDEWEB)

    Grote, Christopher John [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2016-06-07

    Materials Design is often at the forefront of technological innovation. While there has always been a push to generate increasingly low density materials, such as aero or hydrogels, more recently the idea of bicontinuous structures has gone more into play. This review will cover some of the methods and applications for generating both porous, and hierarchically porous structures.

  4. The relevance of metal organic frameworks (MOFs) in inorganic materials chemistry

    Indian Academy of Sciences (India)

    Srinivasan Natarajan; Partha Mahata; Debajit Sarma

    2012-03-01

    The metal organic frameworks (MOFs) have evolved to be an important family and a corner stone for research in the area of inorganic chemistry. The progress made since 2000 has attracted researchers from other disciplines to actively engage themselves in this area. This cooperative synergy of different scientific believes have provided important edge and spread to the chemistry of metal-organic frameworks. The ease of synthesis coupled with the observation of properties in the areas of catalysis, sorption, separation, luminescence, bioactivity, magnetism, etc., are a proof of this synergism. In this article, we present the recent developments in this area.

  5. Porous silicon gettering

    Energy Technology Data Exchange (ETDEWEB)

    Tsuo, Y.S.; Menna, P.; Al-Jassim, M. [National Renewable Energy Lab., Golden, CO (United States)] [and others

    1995-08-01

    We have studied a novel extrinsic gettering method that utilizes the very large surface areas, produced by porous silicon etch on both front and back surfaces of the silicon wafer, as gettering sites. In this method, a simple and low-cost chemical etching is used to generate the porous silicon layers. Then, a high-flux solar furnace (HFSF) is used to provide high-temperature annealing and the required injection of silicon interstitials. The gettering sites, along with the gettered impurities, can be easily removed at the end the process. The porous silicon removal process consists of oxidizing the porous silicon near the end the gettering process followed by sample immersion in HF acid. Each porous silicon gettering process removes up to about 10 {mu}m of wafer thickness. This gettering process can be repeated so that the desired purity level is obtained.

  6. Tunable rare-earth fcu-MOFs: A platform for systematic enhancement of CO2 adsorption energetics and uptake

    KAUST Repository

    Xue, Dongxu

    2013-05-22

    A series of fcu-MOFs based on rare-earth (RE) metals and linear fluorinated/nonfluorinated, homo/heterofunctional ligands were targeted and synthesized. This particular fcu-MOF platform was selected because of its unique structural characteristics combined with the ability/potential to dictate and regulate its chemical properties (e.g., tuning of the electron-rich RE metal ions and high localized charge density, a property arising from the proximal positioning of polarizing tetrazolate moieties and fluoro-groups that decorate the exposed inner surfaces of the confined conical cavities). These features permitted a systematic gas sorption study to evaluate/elucidate the effects of distinctive parameters on CO2-MOF sorption energetics. Our study supports the importance of the synergistic effect of exposed open metal sites and proximal highly localized charge density toward materials with enhanced CO2 sorption energetics. © 2013 American Chemical Society.

  7. UTSA-74: A MOF-74 Isomer with Two Accessible Binding Sites per Metal Center for Highly Selective Gas Separation

    KAUST Repository

    Luo, Feng

    2016-04-26

    A new metal-organic framework Zn2(H2O)-(dobdc)·0.5(H2O) (UTSA-74, H4dobdc = 2,5-dioxido-1,4-benzenedicarboxylic acid), Zn-MOF-74/CPO-27-Zn isomer, has been synthesized and structurally characterized. It has a novel four coordinated fgl topology with one-dimensional channels of about 8.0 Å. Unlike metal sites in the wellestablished MOF-74 with a rod-packing structure in which each of them is in a five coordinate square pyramidal coordination geometry, there are two different Zn2+ sites within the binuclear secondary building units in UTSA-74 in which one of them (Zn1) is in a tetrahedral while another (Zn2) in an octahedral coordination geometry. After activation, the two axial water molecules on Zn2 sites can be removed, generating UTSA-74a with two accessible gas binding sites per Zn2 ion. Accordingly, UTSA-74a takes up a moderately high and comparable amount of acetylene (145 cm3/cm3) to Zn-MOF-74. Interestingly, the accessible Zn2+ sites in UTSA-74a are bridged by carbon dioxide molecules instead of being terminally bound in Zn-MOF-74, so UTSA-74a adsorbs a much smaller amount of carbon dioxide (90 cm3/cm3) than Zn-MOF-74 (146 cm3/cm3) at room temperature and 1 bar, leading to a superior MOF material for highly selective C2H2/CO2 separation. X-ray crystal structures, gas sorption isotherms, molecular modeling, and simulated and experimental breakthroughs comprehensively support this result. © 2016 American Chemical Society.

  8. Quest for highly porous metal-metalloporphyrin framework based upon a custom-designed octatopic porphyrin ligand

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xi-Sen; Chrzanowski, Matthew; Kim, Chungsik; Gao, Wen-Yang; Wojtas, Lukasz; Chen, Yu-Sheng; Zhang, X Peter; Ma, Shengqian [USF; (UC)

    2012-12-13

    A porous metal-metalloporphyrin framework, MMPF-2, has been constructed from a custom-designed octatopic porphyrin ligand, tetrakis(3,5-dicarboxyphenyl)porphine, that links a distorted cobalt trigonal prism secondary building unit. MMPF-2 possesses permanent microporosity with the highest surface area of 2037 mg2 g-1 among reported porphyrin-based MOFs, and demonstrates a high uptake capcity of 170 cm3 g-1 CO2 at 273 K and 1 bar.

  9. Simulations of hydrogen sorption in rht-MOF-1: identifying the binding sites through explicit polarization and quantum rotation calculations

    KAUST Repository

    Pham, Tony

    2014-01-01

    Grand canonical Monte Carlo (GCMC) simulations of hydrogen sorption were performed in rht-MOF-1, a metal-organic framework (MOF) that consists of isophthalate groups joined by copper paddlewheel clusters and Cu3O trimers through tetrazolate moeities. This is a charged rht-MOF that contains extra-framework nitrate counterions within the material. For the simulations performed herein, excellent agreement with experiment was achieved for the simulated hydrogen sorption isotherms and calculated isosteric heat of adsorption, Qst, values only when using a polarizable potential. Thermodynamic agreement is demonstrated via comparing to experimental isotherms and binding sites are revealed by combining simulation and inelastic neutron scattering (INS) data. Simulations involving explicit many-body polarization interactions assisted in the determination of the binding sites in rht-MOF-1 through the distribution of the induced dipoles that led to strong adsorbate interactions. Four distinct hydrogen sorption sites were determined from the polarization distribution: the nitrate ions located in the corners of the truncated tetrahedral cages, the Cu2+ ions of the paddlewheels that project into the truncated tetrahedral and truncated octahedral cages (Cu1 ions), the Cu2+ ions of the Cu3O trimers (Cu3 ions), and the sides of the paddlewheels in the cuboctahedral cage. The simulations revealed that the initial sorption sites for hydrogen in rht-MOF-1 are the nitrate ions; this site corresponds to the high initial Qst value for hydrogen (9.5 kJ mol-1) in the MOF. The radial distribution functions, g(r), about the Cu2+ ions at various loadings revealed that the Cu1 ions are the preferred open-metal sorption sites for hydrogen at low loading, while the Cu3 ions become occupied at higher loadings. The validation of the aforementioned sorption sites in rht-MOF-1 was confirmed by calculating the two-dimensional quantum rotational levels about each site and comparing the levels to the

  10. Effect of pendant isophthalic acid moieties on the adsorption properties of light hydrocarbons in HKUST-1-like tbo -MOFs: Application to methane purification and storage

    KAUST Repository

    Belmabkhout, Youssef

    2014-01-01

    Equilibrium adsorption of methane (CH4), C2+ gases (ethane (C2H6), ethylene (C2H4), propane (C3H8), and propylene (C3H6)), and carbon dioxide (CO2) was measured on a series of tbo-MOFs (topological analogues of the prototypical MOF, HKUST-1, correspondingly dubbed tbo-MOF-1), which were developed via the supermolecular building layer (SBL) pillaring strategy. Specifically, tbo-MOF-2 and its isoreticular, functionalized analogue, tbo-MOF-2-{CH2O[Ph(CO2H)2]}2 (or tbo-MOF-3), which is characterized by pendant isophthalic acid moieties freely pointing into the cavities, were evaluated on the basis of potential use in methane storage and C2+/CH4 separation. The parent, tbo-MOF-2, showed high gravimetric and volumetric CH4 uptake, close to the U.S. Department of Energy (DOE) target for methane storage at 35 bar and room temperature. Though the presence of the pendant isophthalic acid moiety in the analogous compound, tbo-MOF-3, led to a decrease in total CH4 uptake, due mainly to the reduced size of the cavities, interestingly, it increased the affinity of the SBL-based tbo-MOF platform for propane, propene, ethane, and ethylene at low pressures compared with CH4, due additionally to the enhanced interactions of the highly polarizable light hydrocarbons with the isophthalic acid moiety. Using Ideal Adsorption Solution Theory (IAST), the predicted mixture adsorption equilibria for the C3H8/CH4, C3H6/CH4, C2H6/CH4, C2H4/CH4, and C3H8/CO2 systems showed high adsorption selectivity for C2+ over methane for tbo-MOF-3 compared with tbo-MOF-2. The high working storage capacity of tbo-MOF-2 and the high affinity of tbo-MOF-3 for C2+ over CH4 and CO2 make tbo-MOF an ideal platform for studies in gas storage and separation.

  11. Porphyrin-Alkaline Earth MOFs with the Highest Adsorption Capacity for Methylene Blue.

    Science.gov (United States)

    Hou, Yuxia; Sun, Junshan; Zhang, Daopeng; Qi, Dongdong; Jiang, Jianzhuang

    2016-04-25

    A series of four porphyrin-alkaline earth metal- organic frameworks [Mg(HDCPP)2 (DMF)2 ]n ⋅(H2 O)7 n (1), [Ca(HDCPP)2 (H2 O)2 ]n (DMF)1.5 n (2), [Sr(DCPP)(H2 O)(DMA)]n (3), and [Ba(DCPP)(H2 O)(DMA)]n (4) was isolated for the first time from solvothermal reaction between metal-free 5,15-di(4- carboxyphenyl)porphyrin (H2 DCPP) and alkaline earth ions. Single-crystal X-ray diffraction analysis reveals the 2D and 3D supramolecular network with periodic nanosized porosity for 1/2 and 3/4, respectively. The whole series of MOFs, in particular, compounds 1 and 2 with intrinsic low molecular formula weight, exhibit superior adsorption performance for methylene blue (MB) with excellent capture capacity as represented by the thus far highest adsorption amount of 952 mg g(-1) for 2 and good selectivity, opening a new way for the potential application of the main group metal-based MOFs. PMID:27002679

  12. Cation Exchange Strategy for the Encapsulation of a Photoactive CO-Releasing Organometallic Molecule into Anionic Porous Frameworks.

    Science.gov (United States)

    Carmona, Francisco J; Rojas, Sara; Sánchez, Purificación; Jeremias, Hélia; Marques, Ana R; Romão, Carlos C; Choquesillo-Lazarte, Duane; Navarro, Jorge A R; Maldonado, Carmen R; Barea, Elisa

    2016-07-01

    The encapsulation of the photoactive, nontoxic, water-soluble, and air-stable cationic CORM [Mn(tacn)(CO)3]Br (tacn = 1,4,7-triazacyclononane) in different inorganic porous matrixes, namely, the metalorganic framework bio-MOF-1, (NH2(CH3)2)2[Zn8(adeninate)4(BPDC)6]·8DMF·11H2O (BPDC = 4,4'-biphenyldicarboxylate), and the functionalized mesoporous silicas MCM-41-SO3H and SBA-15-SO3H, is achieved by a cation exchange strategy. The CO release from these loaded materials, under simulated physiological conditions, is triggered by visible light. The results show that the silica matrixes, which are unaltered under physiological conditions, slow the kinetics of CO release, allowing a more controlled CO supply. In contrast, bio-MOF-1 instability leads to the complete leaching of the CORM. Nevertheless, the degradation of the MOF matrix gives rise to an enhanced CO release rate, which is related to the presence of free adenine in the solution. PMID:27291890

  13. Magnetic porous carbon nanocomposites derived from metal-organic frameworks as a sensing platform for DNA fluorescent detection.

    Science.gov (United States)

    Tan, Hongliang; Tang, Gonge; Wang, Zhixiong; Li, Qian; Gao, Jie; Wu, Shimeng

    2016-10-12

    Metal-organic frameworks (MOFs) have emerged as very fascinating functional materials due to their tunable nature and diverse applications. In this work, we prepared a magnetic porous carbon (MPC) nanocomposite by employing iron-containing MOFs (MIL-88A) as precursors through a one-pot thermolysis method. It was found that the MPC can absorb selectively single-stranded DNA (ssDNA) probe to form MPC/ssDNA complex and subsequently quench the labelled fluorescent dye of the ssDNA probe, which is resulted from the synergetic effect of magnetic nanoparticles and carbon matrix. Upon the addition of complementary target DNA, however, the absorbed ssDNA probe could be released from MPC surface by forming double-stranded DNA with target DNA, and accompanied by the recovery of the fluorescence of ssDNA probe. Based on these findings, a sensing platform with low background signal for DNA fluorescent detection was developed. The proposed sensing platform exhibits high sensitivity with detection limit of 1 nM and excellent selectivity to specific target DNA, even single-base mismatched nucleotide can be distinguished. We envision that the presented study would provide a new perspective on the potential applications of MOF-derived nanocomposites in biomedical fields. PMID:27662768

  14. Adsorptive removal of methyl orange from aqueous solution with metal-organic frameworks, porous chromium-benzenedicarboxylates

    Energy Technology Data Exchange (ETDEWEB)

    Haque, Enamul; Lee, Ji Eun [Department of Chemistry, Kyungpook National University, Daegu 702-701 (Korea, Republic of); Jang, In Tae; Hwang, Young Kyu; Chang, Jong-San [Research Center for Nanocatalysts, Korea Research Institute of Chemical Technology, P.O. Box, 107, Yusung, Daejeon 305-600 (Korea, Republic of); Jegal, Jonggeon [Membrane and Separation Research Center, Korea Research Institute of Chemical Technology, P.O. Box 107, Yusung, Daejeon 305-600 (Korea, Republic of); Jhung, Sung Hwa, E-mail: sung@knu.ac.kr [Department of Chemistry, Kyungpook National University, Daegu 702-701 (Korea, Republic of)

    2010-09-15

    Two typical highly porous metal-organic framework (MOF) materials based on chromium-benzenedicarboxylates (Cr-BDC) obtained from Material of Institute Lavoisier with special structure of MIL-101 and MIL-53 have been used for the adsorptive removal of methyl orange (MO), a harmful anionic dye, from aqueous solutions. The adsorption capacity and adsorption kinetic constant of MIL-101 are greater than those of MIL-53, showing the importance of porosity and pore size for the adsorption. The performance of MIL-101 improves with modification: the adsorption capacity and kinetic constant are in the order of MIL-101 < ethylenediamine-grafted MIL-101 < protonated ethylenediamine-grafted MIL-101 (even though the porosity and pore size are slightly decreased with grafting and further protonation). The adsorption capacity of protonated ethylenediamine-grafted MIL-101 decreases with increasing the pH of an aqueous MO solution. These results suggest that the adsorption of MO on the MOF is at least partly due to the electrostatic interaction between anionic MO and a cationic adsorbent. Adsorption of MO at various temperatures shows that the adsorption is a spontaneous and endothermic process and that the entropy increases (the driving force of the adsorption) with MO adsorption. The adsorbent MIL-101s are re-usable after sonification in water. Based on this study, MOFs can be suggested as potential re-usable adsorbents to remove anionic dyes because of their high porosity, facile modification and ready re-activation.

  15. Preparation of Zeolitic Imidazolate Framework-8 (ZIF-8) Membrane on Porous Polymeric Support via Contra-Diffusion Method

    KAUST Repository

    Tan, Xiaoyu

    2016-05-18

    In the last decade, many attempts were made to put metal organic frameworks (MOFs) in industrial applications, but most of these efforts weren’t successfully. As one of the few MOFs produced on industrial scale, ZIF-8 has interesting pore size, huge internal surface area and great thermal and chemical stability. Therefore, ZIF-8 might become the first MOF, which will be applied in industrial separation processes. In this thesis, a synthesis study is presented, which leads to a cheap and convenient way to
fabricate defect-free and thin ZIF-8 membranes on porous polymeric supports showing high selectivity and high gas permeance. The ZIF-8 layers were produced via a contra-diffusion method. Several polymeric membranes were employed as support in this study, such as PAN, PEI, PSU, PA and PTSC. We studied the influence of the polymeric support properties for the ZIF-8 membrane preparation and optimized the ZIF-8 preparation conditions. The ZIF-8 membranes were characterized via scanning electron microscopy (SEM) and X-ray diffraction (XRD). For gas permeation test, we chose a Wicke-Kallenbach apparatus to measure membrane’s gas permeance and selectivity. One of the best ZIF-8 membranes exhibited a hydrogen permeance of 3.45 × 10-8 mol m-2 s-1 Pa-1 and
an ideal selectivity of hydrogen over propane of about 500.

  16. Rational design and synthesis of Ni x Co 3−x O 4 nanoparticles derived from multivariate MOF-74 for supercapacitors

    KAUST Repository

    Chen, Siru

    2015-01-01

    © The Royal Society of Chemistry 2015. Mixed transition metal oxides have attracted much attention recently due to their potential application in energy and environmental sciences. The emergence of multivariate MOFs recently has attracted great research attention and provides an opportunity for multivariate mixed-metal oxides. In this work, five isostructural, single-phase MOF-74 structures with different divalent metals (MOF-74-Co, MOF-74-Ni, MOF-74-NiCo1, MOF-74-NiCo2 and MOF-74-NiCo4) were synthesised by varying the mole ratios of Ni/Co mixed-metal ions. After annealing at the appropriate temperature, Co3O4, NiO and three kinds of NixCo3-xO4 mixed-metal oxide nanoparticles with high surface area were easily obtained and the metal ratio was readily controlled, enabling us to systematically investigate the effect of different metal species amounts on the electrochemical properties of the mixed-metal oxide materials. When these metal oxides were used as electrode materials for supercapacitors, we found that the mixed-metal oxides NixCo3-xO4 obtained from bimetallic MOF-74-NiCo structures had obvious advantages compared with the monometallic oxides of MOF-74-Ni and MOF-74-Co. In particular, the NixCo3-xO4-1 with the Ni/Co metal ratio 1:1 exhibited the highest capacitance of 797 F g-1 and excellent cycling stability.

  17. Fabricating porous silicon carbide

    Science.gov (United States)

    Shor, Joseph S. (Inventor); Kurtz, Anthony D. (Inventor)

    1994-01-01

    The formation of porous SiC occurs under electrochemical anodization. A sample of SiC is contacted electrically with nickel and placed into an electrochemical cell which cell includes a counter electrode and a reference electrode. The sample is encapsulated so that only a bare semiconductor surface is exposed. The electrochemical cell is filled with an HF electrolyte which dissolves the SiC electrochemically. A potential is applied to the semiconductor and UV light illuminates the surface of the semiconductor. By controlling the light intensity, the potential and the doping level, a porous layer is formed in the semiconductor and thus one produces porous SiC.

  18. Stochastic porous media equations

    CERN Document Server

    Barbu, Viorel; Röckner, Michael

    2016-01-01

    Focusing on stochastic porous media equations, this book places an emphasis on existence theorems, asymptotic behavior and ergodic properties of the associated transition semigroup. Stochastic perturbations of the porous media equation have reviously been considered by physicists, but rigorous mathematical existence results have only recently been found. The porous media equation models a number of different physical phenomena, including the flow of an ideal gas and the diffusion of a compressible fluid through porous media, and also thermal propagation in plasma and plasma radiation. Another important application is to a model of the standard self-organized criticality process, called the "sand-pile model" or the "Bak-Tang-Wiesenfeld model". The book will be of interest to PhD students and researchers in mathematics, physics and biology.

  19. Combustion within Porous Waste

    OpenAIRE

    Pfahl, Ulrich; Shepherd, Joseph E.; Unal, Cetin

    1998-01-01

    Flammable gases (primarily hydrogen and nitrous oxide but also ammonia and methane) are continuously being generated within the waste contained in the tank farms at Hanford Site. Some portions of the waste are porous and conceivably, a combustion event could occur within the waste due to accidental ignition. This has been postulated as a potential hazard since deflagrations and detonations are observed in laboratory experiments to propagate through combustible gases in porous materials, or ...

  20. Metal filled porous carbon

    Science.gov (United States)

    Gross, Adam F.; Vajo, John J.; Cumberland, Robert W.; Liu, Ping; Salguero, Tina T.

    2011-03-22

    A porous carbon scaffold with a surface and pores, the porous carbon scaffold containing a primary metal and a secondary metal, where the primary metal is a metal that does not wet the surface of the pores of the carbon scaffold but wets the surface of the secondary metal, and the secondary metal is interspersed between the surface of the pores of the carbon scaffold and the primary metal.

  1. Effect of Synthesis Methods Using Renewable PODFA on Structural Characteristics of Metal-Organic Framework (MOF-5)

    Science.gov (United States)

    Othman, S. Z.; Misran, H.; Affendy, W. A.; Mahadi, N. F.

    2016-03-01

    In this work, metal-organic framework (MOF-5) syntheses were successfully synthesized with three different methods namely i) modified direct-mixing method ii) microwave assisted method and iii) autoclave assisted method without using surfactants. Palm oil derived fatty alcohol (PODFA), dodecyl alcohol (C8) was used as renewable non-surfactant template. Four prominent peaks were observed in all three samples attributable to the reflection planes of (200), (220), (400) and (420) of a cubic structure at ca. 2θ = 6.9°, 9.6°, 13.7° and 15.2°. The morphology of MOF-5 produced using modified direct-mixing method was faceted structure with average size of ca. 1 µm. In addition, the morphology of MOF-5 produced using microwave assisted synthesis was cubic structure with average size of ca. 8.34 µm. However, the morphology of MOF-5 using autoclave assisted method was interpenetrated cubic with average size of ca. 22.65 µm.

  2. A SIM-MOF: three-dimensional organisation of single-ion magnets with anion-exchange capabilities.

    Science.gov (United States)

    Baldoví, José J; Coronado, Eugenio; Gaita-Ariño, Alejandro; Gamer, Christoph; Giménez-Marqués, Mónica; Mínguez Espallargas, Guillermo

    2014-08-18

    The formation of a metal-organic framework (MOF) with nodes that have single-molecule magnet (SMM) behaviour has been achieved by using mononuclear lanthanoid analogues, also known as single-ion magnets (SIMs), which enormously simplifies the challenging issue of making SMM-MOFs. Here we present a rational design of a family of MOFs, [Ln(bipyNO)4](TfO)3⋅x solvent (Ln=Tb (1); Dy (2); Ho (3); Er (4); TfO=triflate), in which the lanthanoid centres have an square-antiprismatic coordination environment suitable for SIM behaviour. Magnetic measurements confirm the existence of slow magnetic relaxation typical of SMMs, which has been rationalised by means of a radial effective charge model. In addition, we have explored the incorporation of bulky polyoxometalates (POMs) into the cavities of the SIM-MOF by anion exchange, finding that they do not interfere with the slow magnetic relaxation. This demonstrates the robustness of the frameworks and opens the possibility of incorporating non-innocent anions. PMID:24804629

  3. Removal of hazardous organics from water using metal-organic frameworks (MOFs): plausible mechanisms for selective adsorptions.

    Science.gov (United States)

    Hasan, Zubair; Jhung, Sung Hwa

    2015-01-01

    Provision of clean water is one of the most important issues worldwide because of continuing economic development and the steady increase in the global population. However, clean water resources are decreasing everyday, because of contamination with various pollutants including organic chemicals. Pharmaceutical and personal care products, herbicides/pesticides, dyes, phenolics, and aromatics (from sources such as spilled oil) are typical organics that should be removed from water. Because of their huge porosities, designable pore structures, and facile modification, metal-organic frameworks (MOFs) are used in various adsorption, separation, storage, and delivery applications. In this review, the adsorptive purifications of contaminated water with MOFs are discussed, in order to understand possible applications of MOFs in clean water provision. More importantly, plausible adsorption or interaction mechanisms and selective adsorptions are summarized. The mechanisms of interactions such as electrostatic interaction, acid-base interaction, hydrogen bonding, π-π stacking/interaction, and hydrophobic interaction are discussed for the selective adsorption of organics over MOFs. The adsorption mechanisms will be very helpful not only for understanding adsorptions but also for applications of adsorptions in selective removal, storage, delivery and so on.

  4. Correlation between the Microstructure of Porous Materials and the Adsorption Properties of H2 and D2

    International Nuclear Information System (INIS)

    One of the most challenging tasks toward the full implementation of the hydrogen based economy is the reversible storage of hydrogen for portable applications. Three main approaches have been investigated to store the hydrogen, storage as a compressed gas or a liquid, or through a direct chemical bond between the hydrogen atom and the material. The alternative approach, the most recently investigated, is the storage of hydrogen at cryogenic conditions. Storage by physisorption within porous adsorbents has particular advantages of complete reversibility, the fast refueling time, the low heat evolution, and above all increased safety. The nature of interaction of hydrogen, deuterium, and gas mixtures with porous adsorbents was exploited by performing thermal desorption spectroscopy (TDS) measurements. This sensitive experimental technique gives qualitative information about the different adsorption sites, which show different desorption temperatures depending on the interaction energy. After an appropriate calibration the amount of gas desorbed may be quantified. To gain a more fundamental insight into the available adsorption sites multiple TDS spectra were recorded, corresponding to different surface coverages (in the pressure range of 1 to 700 mbar), and different heating regimes. Different kind of porous adsorbents, conventional carbon-based materials and novel Metal Organic Framework Materials (MOFs), were used to investigate the hydrogen/deuterium physisorption mechanism. For carbon materials an increase in the hydrogen interaction potential was observed for adsorbents with narrow pore size. The confined geometry, where hydrogen simultaneously interacts with all the surrounding adsorbent walls, strengthens the interaction potential with the adsorbate molecule, thus, maximizing the total van der Waals force on the adsorbate. Crystalline MOFs are a new class of porous materials assembled from discrete metal centers, which act as framework nodes, and organic

  5. Encapsulated discrete octameric water cluster, 1D water tape, and 3D water aggregate network in diverse MOFs based on bisimidazolium ligands

    Science.gov (United States)

    Shi, Ruo-Bing; Pi, Min; Jiang, Shuang-Shuang; Wang, Yuan-Yuan; Jin, Chuan-Ming

    2014-08-01

    Four new metal-organic frameworks, [Zn(2-mBIM)2(SO3CF3)2·(H2O)4] (1), [Zn(BMIE)(1,4-BDC)]·(H2O)3 (2), [Cd(BIM)2(OH)(H2O)2(PF6)]·(H2O)4 (3), and [Cd(PA-BIM)2 (ClO4)2]·11.33H2O (4) (2-mBIM = bis(2-methylimidazol-1-yl)methane, BMIE = 1,2-bis[1-(2-methylimidazole)-diethoxy]ethane, BIM = bis(imidazol-1-yl)methane, and PA-BIM = 1,1-bis [(2-phenylazo)imidazol-1-yl]methane) have been prepared and structurally characterized. Complex 1 exhibits an infinite 1D cationic beaded-chain structure, which encapsulated discrete octameric water clusters that are comprised of a chair-like hexameric water cluster with two extra water molecules dangling on two diagonal vertices of the chair. Complex 2 forms a 1D infinite zigzag metal-organic chain structure with a 1D T4(0)A(4) water tape. Complexes 3 show a 2D grid-like sheet structure with the 1D water tape T4(0)A(0)2(0) motif. Complex 4 is a porous 3D MOF with tetrahedron-coordinated Cd(II) centers and trans-conformation PA-BIM ligands. These holes are occupied by a fascinating three-dimensional water clathrate network, which consists of cage-shaped structural tetradecameric water cluster (H2O)14 units and six independent bridged water molecules. The results suggest that the bisimidazolium ligands and anions play crucial roles in the formation of the different host structures and different guest water aggregations. Additionally, the thermal stabilities and photoluminescence spectra of the complexes have been discussed.

  6. Polydimethylsiloxane Coating for a Palladium/MOF Composite: Highly Improved Catalytic Performance by Surface Hydrophobization.

    Science.gov (United States)

    Huang, Gang; Yang, Qihao; Xu, Qiang; Yu, Shu-Hong; Jiang, Hai-Long

    2016-06-20

    Surface wettability of active sites plays a crucial role in the activity and selectivity of catalysts. This report describes modification of surface hydrophobicity of Pd/UiO-66, a composite comprising a metal-organic framework (MOF) and stabilized palladium nanoparticles (NPs), using a simple polydimethylsiloxane (PDMS) coating. The modified catalyst demonstrated significantly improved catalytic efficiency. The approach can be extended to various Pd nanoparticulate catalysts for enhanced activity in reactions involving hydrophobic reactants, as the hydrophobic surface facilitates the enrichment of hydrophobic substrates around the catalytic site. PDMS encapsulation of Pd NPs prevents aggregation of NPs and thus results in superior catalytic recyclability. Additionally, PDMS coating is applicable to a diverse range of catalysts, endowing them with additional selectivity in sieving reactants with different wettability. PMID:27144320

  7. MOF-Derived Tungstated Zirconia as Strong Solid Acids toward High Catalytic Performance for Acetalization.

    Science.gov (United States)

    Wang, Peng; Feng, Jian; Zhao, Yupei; Wang, Shaobin; Liu, Jian

    2016-09-14

    A strong solid acid, tungstated zirconia (WZ), has been prepared first using tungstate immobilized UiO-66 as precursors through a "double-solvent" impregnation method under mild calcination temperature. With moderate W contents, the as-synthesized WZ catalysts possess a high density of acid sites, and the proper heat treatment also has facilely led to a bunch of oligomeric tungsten clusters on stabilized tetragonal ZrO2. The resultant solid acids show an improved catalytic performance toward the benzaldehyde's acetalization in comparison with traditional zirconium hydroxide-prepared WZ. Notably, due to large surface area and additionally introduced strong acid sites, the MOF-derived WZ catalysts afforded conversion up to 86.0%. The facile method endows the WZ catalysts with superior catalytic activities and excellent recyclability, thus opening a new avenue for preparation of metal oxide-based solid superacids and superbases. PMID:27557351

  8. Ambient pressure synthesis of MIL-100(Fe) MOF from homogeneous solution using a redox pathway.

    Science.gov (United States)

    Jeremias, Felix; Henninger, Stefan K; Janiak, Christoph

    2016-05-17

    Micro- to mesoporous iron(iii) trimesate MIL-100(Fe) is a MOF of high interest for numerous applications. With regard to large-scale synthesis, e.g., by continuous flow or the in situ deposition of coatings, a replacement for the conventional, hydrothermal low-yield fluoride-containing synthesis is desirable. In this contribution, we present a method to synthesize crystalline fluoride-free MIL-100(Fe) from iron(iii) nitrate and trimesic acid in zeotropic DMSO/water solution at normal ambient pressure involving a DMSO-nitrate redox pathway. Yields of 72%, surface areas of SBET = 1791 m(2) g(-1) and pore volumes of Vpore = 0.82 cm(3) g(-1) were achieved. PMID:27143562

  9. Detailed magnetic study on the formato-bridged MOFs with anion-tunable magnetic properties

    Institute of Scientific and Technical Information of China (English)

    WANG XinYi; WANG ZheMing; GAO Song

    2012-01-01

    Detailed studies of the structures,magnetic properties and photodimerization of a series of formato-bridged MOFs with the general formula M2(HCOO)3(4,4'-bpe)3(H20)3(X)(4,4'-bpe =4,4'-bipyridylethylene,M =Mn(l-X-),X- =CIO-4,NO-3,BF-4,I-,Br-; M =Co(2-X-),X- =CIO-4,NO-3; M =Zn(3-X-),X- =NO-3)were reported.Careful magnetic measurements on an oriented single crystal of 1-ClO-4 determined the spin-flop magnetic phase diagram and some intrinsic parameters,such as the intralayer coupling J,the anisotropy field HA and the exchange field HE.Different anions can remarkably tune the magnetic properties of l-X-,especially the critical fields of the spin-flop transition.Compound 2-ClO-4 remained paramagnetic down to 2 K.

  10. Metal Hydrides, MOFs, and Carbon Composites as Space Radiation Shielding Mitigators

    Science.gov (United States)

    Atwell, William; Rojdev, Kristina; Liang, Daniel; Hill, Matthew

    2014-01-01

    Recently, metal hydrides and MOFs (Metal-Organic Framework/microporous organic polymer composites - for their hydrogen and methane storage capabilities) have been studied with applications in fuel cell technology. We have investigated a dual-use of these materials and carbon composites (CNT-HDPE) to include space radiation shielding mitigation. In this paper we present the results of a detailed study where we have analyzed 64 materials. We used the Band fit spectra for the combined 19-24 October 1989 solar proton events as the input source term radiation environment. These computational analyses were performed with the NASA high energy particle transport/dose code HZETRN. Through this analysis we have identified several of the materials that have excellent radiation shielding properties and the details of this analysis will be discussed further in the paper.

  11. A homochiral vanadium-salen based cadmium bpdc MOF with permanent porosity as an asymmetric catalyst in solvent-free cyanosilylation.

    Science.gov (United States)

    Bhunia, Asamanjoy; Dey, Subarna; Moreno, José María; Diaz, Urbano; Concepcion, Patricia; Van Hecke, Kristof; Janiak, Christoph; Van Der Voort, Pascal

    2016-01-25

    A homochiral vanadium-salen based MOF with the pcu topology is constructed via in situ synthesis under solvothermal conditions. The synthesized MOF exhibits BET surface areas of 574 m(2) g(-1), showing the highest H2 adsorption capacity (1.05 wt% at 77 K, 1 bar) and the highest CO2 uptake (51 cm(3) g(-1) at 273 K, 1 bar) for currently known salen-based MOFs. This framework shows excellent performance as an asymmetric catalyst in solvent-free cyanosilylation. PMID:26621199

  12. Metal-organic gel templated synthesis of magnetic porous carbon for highly efficient removal of organic dyes.

    Science.gov (United States)

    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.

  13. Fluorocarbon Adsorption in Hierarchical Porous Frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Motkuri, Radha K.; Annapureddy, Harsha V.; Vijayakumar, M.; Schaef, Herbert T.; Martin, P F.; McGrail, B. Peter; Dang, Liem X.; Krishna, Rajamani; Thallapally, Praveen K.

    2014-07-09

    The adsorption behavior of a series of fluorocarbon derivatives was examined on a set of microporous metal organic framework (MOF) sorbents and another set of hierarchical mesoporous MOFs. The microporous M-DOBDC (M = Ni, Co) showed a saturation uptake capacity for R12 of over 4 mmol/g at a very low relative saturation pressure (P/Po) of 0.02. In contrast, the mesoporous MOF MIL-101 showed an exceptionally high uptake capacity reaching over 14 mmol/g at P/Po of 0.4. Adsorption affinity in terms of mass loading and isosteric heats of adsorption were found to generally correlate with the polarizability of the refrigerant with R12 > R22 > R13 > R14 > methane. These results suggest the possibility of exploiting MOFs for separation of azeotropic mixtures of fluorocarbons and use in eco-friendly fluorocarbon-based adsorption cooling and refrigeration applications.

  14. Foams in porous media

    Energy Technology Data Exchange (ETDEWEB)

    Marsden, S.S.

    1986-07-01

    In 1978 a literature search on selective blocking of fluid flow in porous media was done by Professor S.S. Marsden and two of his graduate students, Tom Elson and Kern Huppy. This was presented as SUPRI Report No. TR-3 entitled ''Literature Preview of the Selected Blockage of Fluids in Thermal Recovery Projects.'' Since then a lot of research on foam in porous media has been done on the SUPRI project and a great deal of new information has appeared in the literature. Therefore we believed that a new, up-to-date search should be done on foam alone, one which would be helpful to our students and perhaps of interest to others. This is a chronological survey showing the development of foam flow, blockage and use in porous media, starting with laboratory studies and eventually getting into field tests and demonstrations. It is arbitrarily divided into five-year time periods. 81 refs.

  15. Porous silicon gettering

    Energy Technology Data Exchange (ETDEWEB)

    Tsuo, Y.S.; Menna, P.; Pitts, J.R. [National Renewable Energy Lab., Golden, CO (United States)] [and others

    1996-05-01

    The authors have studied a novel extrinsic gettering method that uses the large surface areas produced by a porous-silicon etch as gettering sites. The annealing step of the gettering used a high-flux solar furnace. They found that a high density of photons during annealing enhanced the impurity diffusion to the gettering sites. The authors used metallurgical-grade Si (MG-Si) prepared by directional solidification casing as the starting material. They propose to use porous-silicon-gettered MG-Si as a low-cost epitaxial substrate for polycrystalline silicon thin-film growth.

  16. Porous block nanofiber composite filters

    Energy Technology Data Exchange (ETDEWEB)

    Ginley, David S.; Curtis, Calvin J.; Miedaner, Alexander; Weiss, Alan J.; Paddock, Arnold

    2016-08-09

    Porous block nano-fiber composite (110), a filtration system (10) and methods of using the same are disclosed. An exemplary porous block nano-fiber composite (110) includes a porous block (100) having one or more pores (200). The porous block nano-fiber composite (110) also includes a plurality of inorganic nano-fibers (211) formed within at least one of the pores (200).

  17. Successful implementation of the stepwise layer-by-layer growth of MOF thin films on confined surfaces: Mesoporous silica foam as a first case study

    KAUST Repository

    Shekhah, Osama

    2012-01-01

    Here we report the successful growth of highly crystalline homogeneous MOF thin films of HKUST-1 and ZIF-8 on mesoporous silica foam, by employing a layer-by-layer (LBL) method. The ability to control and direct the growth of MOF thin films on confined surfaces, using the stepwise LBL method, paves the way for new prospective applications of such hybrid systems. © 2012 The Royal Society of Chemistry.

  18. MOFs 负载镍钼杂多酸簇及其氧化脱硫的研究%Preparation of POM@MOFs composite and application in oxidative desulfurization of DBT

    Institute of Scientific and Technical Information of China (English)

    张会娟; 冯锡兰; 柳云骐; 梁吉雷

    2016-01-01

    以镍钼杂多酸簇为活性组分,将其负载到具有大比表面积的 MOFs 材料 MIL-101上得到一种新的复合材料用于氧化脱硫的研究。结果表明,镍钼杂多酸簇可以在 MIL-101中均匀分散,氧化脱硫效果优异,在催化剂负载量40%,催化剂用量3.3 mg/g,氧硫比为5,反应温度为60℃,反应时间120 min 时,二苯并噻吩脱除率可达到96.1%。%POMs@MOFs composite material was prepared and used in the oxidative desulfurization of DBT,in which nickel-molybdenum polyoxometalates as the active component was supported on MIL-1 01 , a typical MOFs with large specific surface area and good thermal stability.The results show that the nick-el-molybdenum polyoxometalates was well dispersed in MIL-1 01 .The activity of oxidative desulfurization was excellent,catalyst loading 40%,catalyst amount 3.3 mg/g,oxygen∶sulfur =5,reaction temperature 60 ℃,reaction time 1 20 min,and DBT removal rate could reach 96.1 %.

  19. Filtration in Porous Media

    DEFF Research Database (Denmark)

    Yuan, Hao; Shapiro, Alexander

    There is a considerable and ongoing effort aimed at understanding the transport and the deposition of suspended particles in porous media, especially non-Fickian transport and non-exponential deposition of particles. In this work, the influential parameters in filtration models are studied...

  20. Hydrophobic, Porous Battery Boxes

    Science.gov (United States)

    Bragg, Bobby J.; Casey, John E., Jr.

    1995-01-01

    Boxes made of porous, hydrophobic polymers developed to contain aqueous potassium hydroxide electrolyte solutions of zinc/air batteries while allowing air to diffuse in as needed for operation. Used on other types of batteries for in-cabin use in which electrolytes aqueous and from which gases generated during operation must be vented without allowing electrolytes to leak out.

  1. Aptamer-Mediated Up-conversion Core/MOF Shell Nanocomposites for Targeted Drug Delivery and Cell Imaging

    Science.gov (United States)

    Deng, Kerong; Hou, Zhiyao; Li, Xuejiao; Li, Chunxia; Zhang, Yuanxin; Deng, Xiaoran; Cheng, Ziyong; Lin, Jun

    2015-01-01

    Multifunctional nanocarriers for targeted bioimaging and drug delivery have attracted much attention in early diagnosis and therapy of cancer. In this work, we develop a novel aptamer-guided nanocarrier based on the mesoporous metal-organic framework (MOF) shell and up-conversion luminescent NaYF4:Yb3+/Er3+ nanoparticles (UCNPs) core for the first time to achieve these goals. These UCNPs, chosen as optical labels in biological assays and medical imaging, could emit strong green emission under 980 nm laser. The MOF structure based on iron (III) carboxylate materials [MIL-100 (Fe)] possesses high porosity and non-toxicity, which is of great value as nanocarriers for drug storage/delivery. As a unique nanoplatform, the hybrid inorganic-organic drug delivery vehicles show great promising for simultaneous targeted labeling and therapy of cancer cells.

  2. Selective and Efficient Removal of Mercury from Aqueous Media with the Highly Flexible Arms of a BioMOF.

    Science.gov (United States)

    Mon, Marta; Lloret, Francesc; Ferrando-Soria, Jesús; Martí-Gastaldo, Carlos; Armentano, Donatella; Pardo, Emilio

    2016-09-01

    A robust and water-stable metal-organic framework (MOF), featuring hexagonal channels decorated with methionine residues (1), selectively captures toxic species such as CH3 Hg(+) and Hg(2+) from water. 1 exhibits the largest Hg(2+) uptake capacity ever reported for a MOF, decreasing the [Hg(2+) ] and [CH3 Hg(+) ] concentrations in potable water from highly hazardous 10 ppm to the much safer values of 6 and 27 ppb, respectively. Just like with biological systems, the high-performance metal capture also involves a molecular recognition process. Both CH3 Hg(+) and Hg(2+) are efficiently immobilized by specific conformations adopted by the flexible thioether "claws" decorating the pores of 1. This leads to very stable structural conformations reminiscent of those responsible for the biological activity of the enzyme mercury reductase (MR). PMID:27529544

  3. MOFs as multifunctional catalysts: one-pot synthesis of menthol from citronellal over a bifunctional MIL-101 catalyst.

    Science.gov (United States)

    Cirujano, F G; Llabrés i Xamena, F X; Corma, A

    2012-04-14

    A bifunctional MOF catalyst containing coordinatively unsaturated Cr(3+) sites and palladium nanoparticles (Pd@MIL-101) has been used for the cyclization of citronellal to isopulegol and for the one-pot tandem isomerization/hydrogenation of citronellal to menthol. The MOF was found to be stable under the reaction conditions used, and the results obtained indicate that the performance of this bifunctional solid catalyst is comparable with other state-of-the-art materials for the tandem reaction: Full citronellal conversion was attained over Pd@MIL-101 in 18 h, with 86% selectivity to menthols and a diastereoselectivity of 81% to the desired (-)-menthol, while up to 30 h were necessary for attaining similar values over Ir/H-beta under analogous reaction conditions. PMID:22382815

  4. Synthesis and integration of Fe-soc-MOF cubes into colloidosomes via a single-step emulsion-based approach

    KAUST Repository

    Pang, Maolin

    2013-07-17

    Bottom-up fabrication of complex 3D hollow superstructures from nonspherical building blocks (BBs) poses a significant challenge for scientists in materials chemistry and physics. Spherical colloidal silica or polystyrene particles are therefore often integrated as BBs for the preparation of an emerging class of materials, namely colloidosomes (using colloidal particles for Pickering stabilization and fusing them to form a permeable shell). Herein, we describe for the first time a one-step emulsion-based technique that permits the assembly of metal-organic framework (MOF) faceted polyhedral BBs (i.e., cubes instead of spheres) into 3D hollow superstructures (or "colloidosomes" ). The shell of each resultant hollow MOF colloidosome is constructed from a monolayer of cubic BBs, whose dimensions can be precisely controlled by varying the amount of emulsifier used in the synthesis. © 2013 American Chemical Society.

  5. An Efficient Synthesis Strategy for Metal-Organic Frameworks: Dry-Gel Synthesis of MOF-74 Framework with High Yield and Improved Performance.

    Science.gov (United States)

    Das, Atanu Kumar; Vemuri, Rama Sesha; Kutnyakov, Igor; McGrail, B Peter; Motkuri, Radha Kishan

    2016-06-16

    Vapor-assisted dry-gel synthesis of the metal-organic framework-74 (MOF-74) structure, specifically Ni-MOF-74 produced from synthetic precursors using an organic-water hybrid solvent system, showed a very high yield (>90% with respect to 2,5-dihydroxyterepthalic acid) and enhanced performance. The Ni-MOF-74 obtained showed improved sorption characteristics towards CO2 and the refrigerant fluorocarbon dichlorodifluoromethane. Unlike conventional synthesis, which takes 72 hours using the tetrahydrofuran-water system, this kinetic study showed that Ni-MOF-74 forms within 12 hours under dry-gel conditions with similar performance characteristics, and exhibits its best performance characteristics even after 24 hours of heating. In the dry-gel conversion method, the physical separation of the solvent and precursor mixture allows for recycling of the solvent. We demonstrated efficient solvent recycling (up to three times) that resulted in significant cost benefits. The scaled-up manufacturing cost of Ni-MOF-74 synthesized via our dry-gel method is 45% of conventional synthesis cost. Thus, for bulk production of the MOFs, the proposed vapor-assisted, dry-gel method is efficient, simple, and inexpensive when compared to the conventional synthesis method.

  6. An Efficient Synthesis Strategy for Metal-Organic Frameworks: Dry-Gel Synthesis of MOF-74 Framework with High Yield and Improved Performance

    Science.gov (United States)

    Das, Atanu Kumar; Vemuri, Rama Sesha; Kutnyakov, Igor; McGrail, B. Peter; Motkuri, Radha Kishan

    2016-06-01

    Vapor-assisted dry-gel synthesis of the metal-organic framework-74 (MOF-74) structure, specifically Ni-MOF-74 produced from synthetic precursors using an organic-water hybrid solvent system, showed a very high yield (>90% with respect to 2,5-dihydroxyterepthalic acid) and enhanced performance. The Ni-MOF-74 obtained showed improved sorption characteristics towards CO2 and the refrigerant fluorocarbon dichlorodifluoromethane. Unlike conventional synthesis, which takes 72 hours using the tetrahydrofuran-water system, this kinetic study showed that Ni-MOF-74 forms within 12 hours under dry-gel conditions with similar performance characteristics, and exhibits its best performance characteristics even after 24 hours of heating. In the dry-gel conversion method, the physical separation of the solvent and precursor mixture allows for recycling of the solvent. We demonstrated efficient solvent recycling (up to three times) that resulted in significant cost benefits. The scaled-up manufacturing cost of Ni-MOF-74 synthesized via our dry-gel method is 45% of conventional synthesis cost. Thus, for bulk production of the MOFs, the proposed vapor-assisted, dry-gel method is efficient, simple, and inexpensive when compared to the conventional synthesis method.

  7. A supermolecular building layer approach for gas separation and storage applications: The eea and rtl MOF platforms for CO2 capture and hydrocarbon separation

    KAUST Repository

    Chen, Zhijie

    2015-01-01

    The supermolecular building layer (SBL) approach was employed to deliberately synthesize five novel metal-organic frameworks (1-5) with an exposed array of amide or amine functionalities within their pore system. The ability to decorate the pores with nitrogen donor moieties offers potential to evaluate/elucidate the structure-adsorption property relationship. Two MOF platforms, eea-MOF and rtl-MOF, based on pillaring of kgm-a or sql-a layers with heterofunctional 3-connected organic building blocks were targeted and constructed to purposely introduce and expose the desired amide or amine functionalities. Interestingly, gas adsorption properties of eea-MOF-4 (1) and eea-MOF-5 (2) showed that by simply altering the nitrogen donor position within the ligand, it is possible to relatively reduce the pore size of the related eea-MOF material and subsequently increase the associated CO2 uptake. The slightly confined pore space in 2, relative to 1, has enabled an enhancement of the pore local charge density and thus the observed relative increase in the CO2 and H2 isosteric heat of adsorption (Qst). In addition, light hydrocarbon adsorption studies revealed that 2 is more selective toward C2H6 and C3H8 over CH4 than 1, as exemplified for C2H6:CH4 (5:95) or C3H8:CH4 (5:95) binary gas mixtures. This journal is

  8. A supermolecular building layer approach for gas separation and storage applications: the eea and rtl MOF platforms for CO 2 capture and hydrocarbon separation

    KAUST Repository

    Chen, Zhijie

    2015-02-11

    The supermolecular building layer (SBL) approach was employed to deliberately synthesize five novel metal–organic frameworks (1–5) with an exposed array of amide or amine functionalities within their pore system. The ability to decorate the pores with nitrogen donor moieties offers potential to evaluate/elucidate the structure–adsorption property relationship. Two MOF platforms, eea-MOF and rtl-MOF, based on pillaring of kgm-a or sql-a layers with heterofunctional 3-connected organic building blocks were targeted and constructed to purposely introduce and expose the desired amide or amine functionalities. Interestingly, gas adsorption properties of eea-MOF-4 (1) and eea-MOF-5 (2) showed that by simply altering the nitrogen donor position within the ligand, it is possible to relatively reduce the pore size of the related eea-MOF material and subsequently increase the associated CO2 uptake. The slightly confined pore space in 2, relative to 1, has enabled an enhancement of the pore local charge density and thus the observed relative increase in the CO2 and H2 isosteric heat of adsorption (Qst). In addition, light hydrocarbon adsorption studies revealed that 2 is more selective toward C2H6 and C3H8 over CH4 than 1, as exemplified for C2H6 : CH4 (5 : 95) or C3H8 : CH4 (5 : 95) binary gas mixtures.

  9. The development of new materials such MOFs for CO2 capture and alkylation of aromatic compounds

    International Nuclear Information System (INIS)

    This thesis is a European project TOPCOMBI of 22 partners. More specifically, this work is the result of collaboration between ENI (Italy), ITQ (Spain), Repsol (Spain) and IRCELYON (France). This work consists of 2 different themes which improvements can be obtained by finding new materials tailored to the needs. The global energy demands are and will be constantly rising in the coming years. In order to meet this need, new resources must be found and further optimized. Fossil fuels are among the most used resources in the world. Among this 3, natural gas appears to be the most promising point of view of energy efficiency and ecological impact. However, many gas fields cannot be treated because there are too small or too contaminated to be economically viable. One way to make them attractive is to lower the cost of purification using novel separation techniques such as the PSA system. However, there is no currently effective adsorbent to allow a viable economic cleansing. Today, the alkylation reactions represent a very important economic interest. Industrial processes are typically carried out by homogeneous acid reactions or not. Seeing the new environmental restrictions, some homogeneous catalytic processes must be replaced by heterogeneous catalytic reactions with the same yields. To do this, new materials to acid characters were used: the zeolites. However the small size of pores of these compounds prevents selective alkylation reactions of molecules too large compounds such as poly-aromatic. For twenty years, new microporous crystalline compounds have emerged: the MOFs, Metal Organic Frameworks. These compounds have the characteristic to be obtained with different metal cations and organic ligands. These combinations give a wide variety of these compounds at the level of reactivity, pore volume and pore size. In this work, we tried to get different materials with specific characteristics in order to use them in methods for purification of methane in acid

  10. Different magnetic responses observed in Co, Co and Co-based MOFs.

    Science.gov (United States)

    Zhang, Chao; Liu, Zhong-Yi; Liu, Ning; Zhao, Hong; Yang, En-Cui; Zhao, Xiao-Jun

    2016-07-19

    Four magnetic MOFs with anisotropic Co(II) ions, {[Co5(H2O)2(μ3-OH)2(atz)2(stp)2]·1.5H2O}n (1), {[Co5(H2O)2(μ3-OH)2(trz)2(stp)2]·1.3H2O}n (2), {[Co5(H2O)6(μ3-OH)2(trz)2(stp)2]·2.5CH3OH}n (3) and {[Co3(H2O)4(Hdatrz)2(stp)2]·3H2O}n (4) (stp(3-) = 2-sulfoterephthalate, trz(-) = 1,2,4-triazolate, atz(-) = 3-amino-1,2,4-triazolate and Hdatrz = 3,5-diamino-1,2,4-triazole) were solvothermally isolated by varying the substituent groups appended on the N-heterocyclic triazole and structurally and magnetically characterized. Structural analyses indicate that the former two complexes are crystallographically isostructural, exhibiting pillared-layer frameworks with mixed triazolyl and carboxylate extended Co + Co layers supported by rigid stp(3-) connectors. Complex 3 is built from butterfly-shaped Co cluster-based layers, which are interconnected with single cobalt(ii) octahedra by ditopic stp(3-) bridges. By contrast, complex 4 consists of linear {Co3(μ-N1,N4-Hdatrz)2} subunits, which are extended by 3-connected stp(3-) linkers into a stable 3D framework. Magnetically, 1 exhibits ferromagnetic ordering below 2.7 K due to the well-organized alignment of the non-compensated resultant moment from octahedra and tetrahedral cobalt(ii) carriers, while 3 is in a non-zero paramagnetic state above 2.0 K resulting from the coexistence of intermetallic ferromagnetic and antiferromagnetic interactions. The magnetic competition between weak inter-subunit antiferromagnetic interactions and the external magnetic field makes 4 behave as a field-induced metamagnet with a critical field of 27.5 kOe. These interesting magnetostructural results suggest that the anisotropy of the moment carrier and the interlayer/intersubunit separations significantly dominate the magnetic responses in extended MOFs, providing an informative platform for the further development of interesting magnetic materials, both of academic and industrial interest. PMID:27377468

  11. Post-Synthetic Shaping of Porosity and Crystal Structure of Ln-Bipy-MOFs by Thermal Treatment

    Directory of Open Access Journals (Sweden)

    Philipp R. Matthes

    2015-07-01

    Full Text Available The reaction of anhydrous lanthanide chlorides together with 4,4′-bipyridine yields the MOFs 2∞[Ln2Cl6(bipy3]·2bipy, with Ln = Pr − Yb, bipy = 4,4′-bipyridine, and 3∞[La2Cl6(bipy5]·4bipy. Post-synthetic thermal treatment in combination with different vacuum conditions was successfully used to shape the porosity of the MOFs. In addition to the MOFs microporosity, a tuneable mesoporosity can be implemented depending on the treatment conditions as a surface morphological modification. Furthermore, thermal treatment without vacuum results in several identifiable crystalline high-temperature phases. Instead of collapse of the frameworks upon heating, further aggregation under release of bipy is observed. 3∞[LaCl3(bipy] and 2∞[Ln3Cl9(bipy3], with Ln = La, Pr, Sm, and 1∞[Ho2Cl6(bipy2] were identified and characterized, which can also exhibit luminescence. Besides being released upon heating, the linker 4,4′-bipyridine can undergo activation of C-C bonding in ortho-position leading to the in-situ formation of 4,4′:2′,2′′:4′′,4′′′-quaterpyridine (qtpy. qtpy can thereby function as linker itself, as shown for the formation of the network 2∞[Gd2Cl6(qtpy2(bipy2]·bipy. Altogether, the manuscript elaborates the influence of thermal treatment beyond the usual activation procedures reported for MOFs.

  12. On demand: The singular rht net, an ideal blueprint for the construction of a metal-organic framework (mof) platform

    KAUST Repository

    Eubank, Jarrod F.

    2012-09-07

    The exceptional nature of the rht-MOF platform, based on a singular edge-transitive net (the only net for the combination of 3- and 24-connected nodes), makes it an ideal target in crystal chemistry. The high level of control indicates an unparalleled blueprint for isoreticular functional materials (without concern for interpenetration) for targeted applications. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Origins and Evolution of Inorganic-Based and MOF-Based Mixed-Matrix Membranes for Gas Separations

    Directory of Open Access Journals (Sweden)

    Edson V. Perez

    2016-09-01

    Full Text Available Gas separation for industrial, energy, and environmental applications requires low energy consumption and small footprint technology to minimize operating and capital costs for the processing of large volumes of gases. Among the separation methods currently being used, like distillation, amine scrubbing, and pressure and temperature swing adsorption, membrane-based gas separation has the potential to meet these demands. The key component, the membrane, must then be engineered to allow for high gas flux, high selectivity, and chemical and mechanical stability at the operating conditions of feed composition, pressure, and temperature. Among the new type of membranes studied that show promising results are the inorganic-based and the metal-organic framework-based mixed-matrix membranes (MOF-MMMs. A MOF is a unique material that offers the possibility of tuning the porosity of a membrane by introducing diffusional channels and forming a compatible interface with the polymer. This review details the origins of these membranes and their evolution since the first inorganic/polymer and MOF/polymer MMMs were reported in the open literature. The most significant advancements made in terms of materials, properties, and testing conditions are described in a chronological fashion.

  14. Metal-Organic Frameworks (MOFs) of a Cubic Metal Cluster with Multicentered Mn(I)-Mn(I) Bonds.

    Science.gov (United States)

    Hu, Huan-Cheng; Hu, Han-Shi; Zhao, Bin; Cui, Ping; Cheng, Peng; Li, Jun

    2015-09-28

    MOFs with both multicentered metal-metal bonds and low-oxidation-state (LOS) metal ions have been underexplored hitherto. Here we report the first cubic [Mn(I) 8 ] cluster-based MOF (1) with multicentered Mn(I)-Mn(I) bonds and +1 oxidation state of manganese (Mn(I) or Mn(I)), as is supported by single-crystal structure determination, XPS analyses, and quantum chemical studies. Compound 1 possesses the shortest Mn(I)-Mn(I) bond of 2.372 Å. Theoretical studies with density functional theory (DFT) reveal extensive electron delocalization over the [Mn(I) 8 ] cube. The 48 electrons in the [Mn(I) 8 ] cube fully occupy half of the 3d-based and the lowest 4s-based bonding orbitals, with six electrons lying at the nonbonding 3d-orbitals. This bonding feature renders so-called cubic aromaticity. Magnetic properties measurements show that 1 is an antiferromagnet. This work is expected to inspire further investigation of cubic metal-metal bonding, MOF materials with LOS metals, and metalloaromatic theory.

  15. Molecular simulation of gas adsorption and diffusion in a breathing MOF using a rigid force field

    NARCIS (Netherlands)

    García-Pérez, E.; Serra-Crespo,P.; Hamad, S.; Kapteijn, F.; Gascon, J.

    2014-01-01

    Simulation of gas adsorption in flexible porous materials is still limited by the slow progress in the development of flexible force fields. Moreover, the high computational cost of such flexible force fields may be a drawback even when they are fully developed. In this work, molecular simulations o

  16. MOF-Based Membrane Encapsulated ZnO Nanowires for Enhanced Gas Sensor Selectivity.

    Science.gov (United States)

    Drobek, Martin; Kim, Jae-Hun; Bechelany, Mikhael; Vallicari, Cyril; Julbe, Anne; Kim, Sang Sub

    2016-04-01

    Gas sensors are of a great interest for applications including toxic or explosive gases detection in both in-house and industrial environments, air quality monitoring, medical diagnostics, or control of food/cosmetic properties. In the area of semiconductor metal oxides (SMOs)-based sensors, a lot of effort has been devoted to improve the sensing characteristics. In this work, we report on a general methodology for improving the selectivity of SMOx nanowires sensors, based on the coverage of ZnO nanowires with a thin ZIF-8 molecular sieve membrane. The optimized ZnO@ZIF-8-based nanocomposite sensor shows markedly selective response to H2 in comparison with the pristine ZnO nanowires sensor, while showing the negligible sensing response to C7H8 and C6H6. This original MOF-membrane encapsulation strategy applied to nanowires sensor architecture pave the way for other complex 3D architectures and various types of applications requiring either gas or ion selectivity, such as biosensors, photo(catalysts), and electrodes. PMID:27003470

  17. Solvent-Driven Gate Opening in MOF-76-Ce: Effect on CO2 Adsorption.

    Science.gov (United States)

    Ethiraj, Jayashree; Bonino, Francesca; Vitillo, Jenny G; Lomachenko, Kirill A; Lamberti, Carlo; Reinsch, Helge; Lillerud, Karl Petter; Bordiga, Silvia

    2016-04-01

    A cerium-based metal-organic framework with MOF-76 topology has been synthesized by a very simple and fast solvothermal method that has been tested for a one gram yield. Variable-temperature powder XRD and X-ray absorption data, analyzed by Rietveld and multiple-scattering extended X-ray absorption fine-structure methods, revealed high thermal stability and the presence of three different stable structures. X-ray absorption near-edge structure and FTIR spectroscopy probed the presence of cerium(III), which was characterized by coordinatively unsaturated sites that, however, played no major role in carbon dioxide adsorption. The material revealed excellent carbon dioxide adsorption properties: the highest gravimetric capacity of 15 wt% was observed at 1.1 bar in the case of the sample activated at 250 °C in vacuum, whereas the strongest interaction energy of 35 kJ mol(-1) was observed for the sample activated at 150 °C. Negligible nitrogen uptake of the sample activated at 150 °C indicates that this material is a promising candidate for nitrogen/carbon dioxide separation purposes.

  18. Hydrocarbons adsorption on metal trimesate MOFs: Inverse gas chromatography and immersion calorimetry studies

    International Nuclear Information System (INIS)

    Highlights: • Inverse gas chromatography and immersion calorimetry were compared on two MOFs. • Adsorption of seven carbon atoms adsorbates on Cu3(BTC)2 and Fe(BTC) was performed. • Size and polarizability of adsorbates are decisive in the strength of adsorption. • Dispersive interaction of surface free energy depends on the surface area. • Isp is influenced by the chemistry of adsorbates and morphology of the adsorbents. - Abstract: Two commercial metal-organic frameworks, Cu3(BTC)2 and Fe(BTC), have been selected to compare the adsorption parameters obtained on these materials by two different techniques: immersion calorimetry and inverse gas chromatography (IGC), in order to find a relationship between thermodynamic parameters obtained by so different techniques. From comparison between the enthalpy of adsorption obtained from IGC and the enthalpy of immersion, three molecules of the same number of carbon atoms have been selected: n-heptane, methylcyclohexane and toluene. Both by IGC and immersion calorimetry, the interaction is stronger in Fe(BTC), being the aromaticity of TOL determinant in the strength of the interaction. However, splitting of the enthalpy of adsorption into the dispersive and specific components allows to deduce that both parameters are more important on the Cu3(BTC)2, due to the higher available surface area in the case of the dispersive interaction; and for the specific interaction, due to the high potential of interaction into the micropores

  19. Hydrocarbons adsorption on metal trimesate MOFs: Inverse gas chromatography and immersion calorimetry studies

    Energy Technology Data Exchange (ETDEWEB)

    Gutiérrez, Inés; Díaz, Eva; Vega, Aurelio [Department of Chemical and Environmental Engineering, University of Oviedo, Faculty of Chemistry, Julián Clavería s/n, 33006 Oviedo (Spain); Ordóñez, Salvador, E-mail: sordonez@uniovi.es [Department of Chemical and Environmental Engineering, University of Oviedo, Faculty of Chemistry, Julián Clavería s/n, 33006 Oviedo (Spain); Guerrero-Ruiz, Antonio [Department of Inorganic and technical Chemistry, UNED, 28040 Madrid (Spain); Castillejos-López, Eva; Rodríguez-Ramos, Inmaculada [Instituto de Catálisis y Petroleoquímica, CSIC, Madrid (Spain)

    2015-02-20

    Highlights: • Inverse gas chromatography and immersion calorimetry were compared on two MOFs. • Adsorption of seven carbon atoms adsorbates on Cu{sub 3}(BTC){sub 2} and Fe(BTC) was performed. • Size and polarizability of adsorbates are decisive in the strength of adsorption. • Dispersive interaction of surface free energy depends on the surface area. • I{sup sp} is influenced by the chemistry of adsorbates and morphology of the adsorbents. - Abstract: Two commercial metal-organic frameworks, Cu{sub 3}(BTC){sub 2} and Fe(BTC), have been selected to compare the adsorption parameters obtained on these materials by two different techniques: immersion calorimetry and inverse gas chromatography (IGC), in order to find a relationship between thermodynamic parameters obtained by so different techniques. From comparison between the enthalpy of adsorption obtained from IGC and the enthalpy of immersion, three molecules of the same number of carbon atoms have been selected: n-heptane, methylcyclohexane and toluene. Both by IGC and immersion calorimetry, the interaction is stronger in Fe(BTC), being the aromaticity of TOL determinant in the strength of the interaction. However, splitting of the enthalpy of adsorption into the dispersive and specific components allows to deduce that both parameters are more important on the Cu{sub 3}(BTC){sub 2}, due to the higher available surface area in the case of the dispersive interaction; and for the specific interaction, due to the high potential of interaction into the micropores.

  20. Ion conductivity and transport by porous coordination polymers and metal-organic frameworks.

    Science.gov (United States)

    Horike, Satoshi; Umeyama, Daiki; Kitagawa, Susumu

    2013-11-19

    Ion conduction and transport in solids are both interesting and useful and are found in widely distinct materials, from those in battery-related technologies to those in biological systems. Scientists have approached the synthesis of ion-conductive compounds in a variety of ways, in the areas of organic and inorganic chemistry. Recently, based on their ion-conducting behavior, porous coordination polymers (PCPs) and metal-organic frameworks (MOFs) have been recognized for their easy design and the dynamic behavior of the ionic components in the structures. These PCP/MOFs consist of metal ions (or clusters) and organic ligands structured via coordination bonds. They could have highly concentrated mobile ions with dynamic behavior, and their characteristics have inspired the design of a new class of ion conductors and transporters. In this Account, we describe the state-of-the-art of studies of ion conductivity by PCP/MOFs and nonporous coordination polymers (CPs) and offer future perspectives. PCP/MOF structures tend to have high hydrophilicity and guest-accessible voids, and scientists have reported many water-mediated proton (H(+)) conductivities. Chemical modification of organic ligands can change the hydrated H(+) conductivity over a wide range. On the other hand, the designable structures also permit water-free (anhydrous) H(+) conductivity. The incorporation of protic guests such as imidazole and 1,2,4-triazole into the microchannels of PCP/MOFs promotes the dynamic motion of guest molecules, resulting in high H(+) conduction without water. Not only the host-guest systems, but the embedding of protic organic groups on CPs also results in inherent H(+) conductivity. We have observed high H(+) conductivities under anhydrous conditions and in the intermediate temperature region of organic and inorganic conductors. The keys to successful construction are highly mobile ionic species and appropriate intervals of ion-hopping sites in the structures. Lithium (Li

  1. Strong, Lightweight, Porous Materials

    Science.gov (United States)

    Leventis, Nicholas; Meador, Mary Ann B.; Johnston, James C.; Fabrizio, Eve F.; Ilhan, Ulvi

    2007-01-01

    A new class of strong, lightweight, porous materials has been invented as an outgrowth of an effort to develop reinforced silica aerogels. The new material, called X-Aerogel is less hygroscopic, but no less porous and of similar density to the corresponding unmodified aerogels. However, the property that sets X-Aerogels apart is their mechanical strength, which can be as much as two and a half orders of magnitude stronger that the unmodified aerogels. X-Aerogels are envisioned to be useful for making extremely lightweight, thermally insulating, structural components, but they may also have applications as electrical insulators, components of laminates, catalyst supports, templates for electrode materials, fuel-cell components, and filter membranes.

  2. Convection in Porous Media

    CERN Document Server

    Nield, Donald A

    2013-01-01

    Convection in Porous Media, 4th Edition, provides a user-friendly introduction to the subject, covering a wide range of topics, such as fibrous insulation, geological strata, and catalytic reactors. The presentation is self-contained, requiring only routine mathematics and the basic elements of fluid mechanics and heat transfer. The book will be of use not only to researchers and practicing engineers as a review and reference, but also to graduate students and others entering the field. The new edition features approximately 1,750 new references and covers current research in nanofluids, cellular porous materials, strong heterogeneity, pulsating flow, and more. Recognized as the standard reference in the field Includes a comprehensive, 250-page reference list Cited over 2300 times to date in its various editions Serves as an introduction for those entering the field and as a comprehensive reference for experienced researchers Features new sections on nanofluids, carbon dioxide sequestration, and applications...

  3. Subunit Composition and Substrate Specificity of a MOF-containing Histone Acetyltransferase Distinct from the Male-specific Lethal (MSL) Complex*

    Science.gov (United States)

    Cai, Yong; Jin, Jingji; Swanson, Selene K.; Cole, Michael D.; Choi, Seung Hyuk; Florens, Laurence; Washburn, Michael P.; Conaway, Joan W.; Conaway, Ronald C.

    2010-01-01

    Human MOF (MYST1), a member of the MYST (Moz-Ybf2/Sas3-Sas2-Tip60) family of histone acetyltransferases (HATs), is the human ortholog of the Drosophila males absent on the first (MOF) protein. MOF is the catalytic subunit of the male-specific lethal (MSL) HAT complex, which plays a key role in dosage compensation in the fly and is responsible for a large fraction of histone H4 lysine 16 (H4K16) acetylation in vivo. MOF was recently reported to be a component of a second HAT complex, designated the non-specific lethal (NSL) complex (Mendjan, S., Taipale, M., Kind, J., Holz, H., Gebhardt, P., Schelder, M., Vermeulen, M., Buscaino, A., Duncan, K., Mueller, J., Wilm, M., Stunnenberg, H. G., Saumweber, H., and Akhtar, A. (2006) Mol. Cell 21, 811–823). Here we report an analysis of the subunit composition and substrate specificity of the NSL complex. Proteomic analyses of complexes purified through multiple candidate subunits reveal that NSL is composed of nine subunits. Two of its subunits, WD repeat domain 5 (WDR5) and host cell factor 1 (HCF1), are shared with members of the MLL/SET family of histone H3 lysine 4 (H3K4) methyltransferase complexes, and a third subunit, MCRS1, is shared with the human INO80 chromatin-remodeling complex. In addition, we show that assembly of the MOF HAT into MSL or NSL complexes controls its substrate specificity. Although MSL-associated MOF acetylates nucleosomal histone H4 almost exclusively on lysine 16, NSL-associated MOF exhibits a relaxed specificity and also acetylates nucleosomal histone H4 on lysines 5 and 8. PMID:20018852

  4. Coumarin-modified microporous-mesoporous Zn-MOF-74 showing ultra-high uptake capacity and photo-switched storage/release of U(VI) ions.

    Science.gov (United States)

    Zhang, Le; Wang, Lin Lin; Gong, Le Le; Feng, Xue Feng; Luo, Ming Biao; Luo, Feng

    2016-07-01

    Driven by an energy crisis but consequently puzzled by various environmental problems, uranium, as the basic material of nuclear energy, is now receiving extensive attentions. In contrast to numerous sorbents applied in this field, metal-organic framework (MOFs), as a renovated material platform, has only recently been developed. How to improve the adsorption capacity of MOF materials towards U(VI) ions, as well as taking advantage of the nature of these MOFs to design photo-switched behaviour for photo-triggered storage/release of U(VI) ions are at present urgent problems and great challenges to be solved. Herein, we show a simple and facile method to target the goal. Through coordination-based post-synthetic strategy, microporous- mesoporous Zn-MOF-74 was easily functionalized by grafting coumarin on coordinatively unsaturated Zn(II) centers, yielding a series of coumarin-modified Zn-MOF-74 materials. The obtained samples displayed ultra-high adsorption capacity for U(VI) ions from water at pH value of 4 with maximum adsorption capacities as high as 360 mg/g (the record value in MOFs) and a remarkable photo-switched capability of 50 mg/g at pH value of 4. To the best of knowledge, and in contrast to the well-known photo-switched behaviour towards CO2, dye (propidium iodide), as well as fluorescence observed in MOFs, this is the first study that shows a photo-switched behaviour towards radioactive U(VI) ions in aqueous solution.

  5. Understanding Hydrogen Sorption in In- soc -MOF: A Charged Metal-Organic Framework with Open-Metal Sites, Narrow Channels, and Counterions

    KAUST Repository

    Pham, Tony

    2015-03-04

    © 2015 American Chemical Society. Grand canonical Monte Carlo (GCMC) simulations of hydrogen sorption were performed in In-soc-MOF, a charged metal-organic framework (MOF) that contains In3O trimers coordinated to 5,5′-azobis(1,3-benzenedicarboxylate) linkers. The MOF contains nitrate counterions that are located in carcerand-like capsules of the framework. This MOF was shown to have a high hydrogen uptake at 77 K and 1.0 atm. The simulations were performed with a potential that includes explicit many-body polarization interactions, which were important for modeling gas sorption in a charged/polar MOF such as In-soc-MOF. The simulated hydrogen sorption isotherms were in good agreement with experiment in this challenging platform for modeling. The simulations predict a high initial isosteric heat of adsorption, Qst, value of about 8.5 kJ mol-1, which is in contrast to the experimental value of 6.5 kJ mol-1 for all loadings. The difference in the Qst behavior between experiment and simulation is attributed to the fact that, in experimental measurements, the sorbate molecules cannot access the isolated cages containing the nitrate ions, the most energetically favorable site in the MOF, at low pressures due to an observed diffusion barrier. In contrast, the simulations were able to capture the sorption of hydrogen onto the nitrate ions at low loading due to the equilibrium nature of GCMC simulations. The experimental Qst values were reproduced in simulation by blocking access to all of the nitrate ions in the MOF. Furthermore, at 77 K, the sorbed hydrogen molecules were reminiscent of a dense fluid in In-soc-MOF starting at approximately 5.0 atm, and this was verified by monitoring the isothermal compressibility, βT, values. The favorable sites for hydrogen sorption were identified from the polarization distribution as the nitrate ions, the In3O trimers, and the azobenzene

  6. Photochemistry in a 3D metal-organic framework (MOF): monitoring intermediates and reactivity of the fac-to-mer photoisomerization of Re(diimine)(CO)3Cl incorporated in a MOF.

    Science.gov (United States)

    Easun, Timothy L; Jia, Junhua; Calladine, James A; Blackmore, Danielle L; Stapleton, Christopher S; Vuong, Khuong Q; Champness, Neil R; George, Michael W

    2014-03-01

    The mechanism and intermediates in the UV-light-initiated ligand rearrangement of fac-Re(diimine)(CO)3Cl to form the mer isomer, when incorporated into a 3D metal-organic framework (MOF), have been investigated. The structure hosting the rhenium diimine complex is a 3D network with the formula {Mn(DMF)2[LRe(CO)3Cl]}∞ (ReMn; DMF = N,N-dimethylformamide), where the diimine ligand L, 2,2'-bipyridine-5,5'-dicarboxylate, acts as a strut of the MOF. The incorporation of ReMn into a KBr disk allows spatial distribution of the mer-isomer photoproduct in the disk to be mapped and spectroscopically characterized by both Fourier transform infrared and Raman microscopy. Photoisomerization has been monitored by IR spectroscopy and proceeds via dissociation of a CO to form more than one dicarbonyl intermediate. The dicarbonyl species are stable in the solid state at 200 K. The photodissociated CO ligand appears to be trapped within the crystal lattice and, upon warming above 200 K, readily recombines with the dicarbonyl intermediates to form both the fac-Re(diimine)(CO)3Cl starting material and the mer-Re(diimine)(CO)3Cl photoproduct. Experiments over a range of temperatures (265-285 K) allow estimates of the activation enthalpy of recombination for each process of ca. 16 (±6) kJ mol(-1) (mer formation) and 23 (±4) kJ mol(-1) (fac formation) within the MOF. We have compared the photochemistry of the ReMn MOF with a related alkane-soluble Re(dnb)(CO)3Cl complex (dnb = 4,4'-dinonyl-2,2'-bipyridine). Time-resolved IR measurements clearly show that, in an alkane solution, the photoinduced dicarbonyl species again recombines with CO to both re-form the fac-isomer starting material and form the mer-isomer photoproduct. Density functional theory calculations of the possible dicarbonyl species aids the assignment of the experimental data in that the ν(CO) IR bands of the CO loss intermediate are, as expected, shifted to lower energy when the metal is bound to DMF rather than to an

  7. Surfactant-thermal method to synthesize a new Zn(II)-trimesic MOF with confined Ru(bpy){sub 3}{sup 2+} complex

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Hui [State Key Laboratory of Silicon Materials, Department of Materials Science and Engineering, Cyrus Tang Center for Sensor Materials and Applications, Zhejiang University, Hangzhou 310027 (China); Gao, Junkuo, E-mail: jkgao@zstu.edu.cn [The Key laboratory of Advanced Textile Materials and Manufacturing Technology of Ministry of Education, National Engineering Lab for Textile Fiber Materials and Processing Technology (Zhejiang), College of Materials and Textiles, Zhejiang Sci-Tech University, Hangzhou 310018 (China); Wang, Jiangpeng; Qian, Xuefeng [The Key laboratory of Advanced Textile Materials and Manufacturing Technology of Ministry of Education, National Engineering Lab for Textile Fiber Materials and Processing Technology (Zhejiang), College of Materials and Textiles, Zhejiang Sci-Tech University, Hangzhou 310018 (China); Song, Ruijing; Cui, Yuanjing; Yang, Yu [State Key Laboratory of Silicon Materials, Department of Materials Science and Engineering, Cyrus Tang Center for Sensor Materials and Applications, Zhejiang University, Hangzhou 310027 (China); Qian, Guodong, E-mail: gdqian@zju.edu.cn [State Key Laboratory of Silicon Materials, Department of Materials Science and Engineering, Cyrus Tang Center for Sensor Materials and Applications, Zhejiang University, Hangzhou 310027 (China)

    2015-03-15

    A surfactant-thermal method was used to prepare a new zinc-1,3,5-benzentricarboxylate-based metal-organic framework (ZJU-100) with confined Ru(bpy){sub 3}{sup 2+} (RuBpy) complex by using surfactant PEG 400 as reaction medium. The RuBpy molecules were encapsulated between the 2-D sheets in ZJU-100. ZJU-100 showed bathochromic shift in the steady-state emission spectrum and increased emission lifetimes relative to RuBpy molecules. The extended lifetime is attributed to the reduced nonradiative decay rate due to the stabilization of RuBpy within the rigid MOF framework. These results represent the first example of MOF with confined complex synthesized by surfactant, indicating that the surfactant-thermal method could offer exciting opportunities for preparing new MOFs host/guest materials with novel structures and interesting luminescent properties. - Graphical abstract: A surfactant-thermal method was used to prepare a new zinc-1,3,5-benzentricarboxylate-based metal-organic framework (ZJU-100) with confined Ru(bpy){sub 3}{sup 2+} (RuBpy) complex by using surfactant PEG 400 as reaction medium. - Highlights: • Surfactant-thermal synthesis of crystalline metal-organic framework host/guest materials. • RuBpy molecules were encapsulated between the 2-D sheets of MOFs. • Extended lifetime is observed due to the stabilization of RuBpy within the rigid MOF framework.

  8. Preparation and Characterization of a Hydrophobic Metal-Organic Framework Membrane Supported on Thin Porous Metal Sheet

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Jian; Canfield, Nathan L.; Liu, Wei

    2016-02-29

    A hydrophobic metal-organic framework (MOF) UiO-66-CH3 is prepared and its solvothermal stability is investigated in comparison to UiO-66. It is confirmed that the MOF stability is enhanced by introduction of the two methyl groups, while the water adsorption is reduced. Given its hydrophobicity and stability, UiO-66-CH3 is proposed as an attractive membrane material for gas separation under moisture conditions. The UiO-66-CH3 membrane is prepared on a 50µm-thin porous Ni support sheet for the first time by use of a secondary growth method. It is found that uniform seed coating on the support is necessary to form a continuous membrane. In addition to growth time and temperature, presence of a modulator in the growth solution is found to be useful for controlling hydrothermal membrane growth on the seeded support. A dense, inter-grown membrane layer is formed by 24-h growth over a temperature range from 120 oC to 160 oC. The membrane surface comprises 500 nm octahedral crystals, which are supposed to grow out of the original 100 nm spherical seeding crystals. The separation characteristics of resulting membranes are tested with pure CO2, air, CO2/air mixture, and humid CO2/air mixture. CO2 permeance as high as 1.9E-06 mol/m2/s/Pa at 31oC is obtained. Unlike the hydrophilic zeolite membranes, CO2 permeation through this membrane is not blocked by the presence of water vapor in the feed gas. The results suggest that this MOF framework is a promising membrane material worth to be further investigated for separation of CO2 and other small molecules from humid gas mixtures.

  9. Preparation and characteristics of porous ceramics

    Institute of Scientific and Technical Information of China (English)

    Dongmei SHAO; Peiping ZHANG; Liyan MA; Juanjuan LIU

    2007-01-01

    Pyrophyllite is always used for making porous ceramics. In order to design the preparation technics of porous ceramics with pyrophyllite reasonably we must know the classifications, characteristics, properties and applications of porous ceramics. The classification and characteristics of porous ceramics are reviewed in this article; and several common preparations with their advantages and disadvantages are also introduced. The authors discussed the problems existing in researching and developing process for porous ceramics, and forecasted the development prospect of porous ceramics.

  10. An efficient combination of Zr-MOF and microwave irradiation in catalytic Lewis acid Friedel-Crafts benzoylation.

    Science.gov (United States)

    Doan, Tan L H; Dao, Thong Q; Tran, Hai N; Tran, Phuong H; Le, Thach N

    2016-05-01

    A zirconium-based metal-organic framework, an effective heterogeneous catalyst, has been developed for the Friedel-Crafts benzoylation of aromatic compounds under microwave irradiation. Constructed by a Zr(iv) cluster and a linker 1,4-bis(2-[4-carboxyphenyl]ethynyl)benzene (H2CPEB), the MOF, possessing large pores and high chemical stability, was appropriate for the enhancement of Lewis acid activity under microwave irradiation. The reaction studies demonstrated that the material could give high yields for a few minutes and maintain its reactivity and structure over several cycles. PMID:27064371

  11. Fullerene-doped porous glasses

    Science.gov (United States)

    Joshi, M. P.; Kukreja, L. M.; Rustagi, K. C.

    We report the doping of C60 in porous glass by diffusion in solution phase at room temperature. The presence of C60 in the doped porous glass was confirmed spectroscopically. We also report the changes in optical absorption spectrum and intensity-dependent transmission of 30 ns laser pulses at 527 nm in these materials.

  12. Fullerene-doped porous glasses

    Energy Technology Data Exchange (ETDEWEB)

    Joshi, M.P. [Center for Adv. Technol., Indore (India). Nonlinear Optics Group; Kukreja, L.M. [Center for Adv. Technol., Indore (India). Nonlinear Optics Group; Rustagi, K.C. [Center for Adv. Technol., Indore (India). Nonlinear Optics Group

    1997-07-01

    We report the doping of C{sub 60} in porous glass by diffusion in solution phase at room temperature. The presence of C{sub 60} in the doped porous glass was confirmed spectroscopically. We also report the changes in optical absorption spectrum and intensity-dependent transmission of 30 ns laser pulses at 527 nm in these materials. (orig.)

  13. Wetting of porous solids.

    Science.gov (United States)

    Patkar, Saket; Chaudhuri, Parag

    2013-09-01

    This paper presents a simple, three stage method to simulate the mechanics of wetting of porous solid objects, like sponges and cloth, when they interact with a fluid. In the first stage, we model the absorption of fluid by the object when it comes in contact with the fluid. In the second stage, we model the transport of absorbed fluid inside the object, due to diffusion, as a flow in a deforming, unstructured mesh. The fluid diffuses within the object depending on saturation of its various parts and other body forces. Finally, in the third stage, oversaturated parts of the object shed extra fluid by dripping. The simulation model is motivated by the physics of imbibition of fluids into porous solids in the presence of gravity. It is phenomenologically capable of simulating wicking and imbibition, dripping, surface flows over wet media, material weakening, and volume expansion due to wetting. The model is inherently mass conserving and works for both thin 2D objects like cloth and for 3D volumetric objects like sponges. It is also designed to be computationally efficient and can be easily added to existing cloth, soft body, and fluid simulation pipelines. PMID:23846102

  14. Liquid-Phase Epitaxy Effective Encapsulation of Lanthanide Coordination Compounds into MOF Film with Homogeneous and Tunable White-Light Emission.

    Science.gov (United States)

    Gu, Zhi-Gang; Chen, Zheng; Fu, Wen-Qiang; Wang, Fei; Zhang, Jian

    2015-12-30

    As a new family of hybrid inorganic-organic materials with large porosity, metal-organic frameworks (MOFs) have received attractive attention recently on encapsulating functional guest species. Although the encapsulation of luminescent guest into bulk MOFs can tune the luminescent property, the powder composite materials are limited to the application in optical sensors and devices. In the present work, we use a modified liquid-phase epitaxial (LPE) pump method for the fabrication of lanthanide coordination compounds (LCCs)-encapsulated MOF thin film on substrate with high encapsulation efficiency. The resultant composite film reveals an oriented and homogeneous composite film, in which a white light emission by tuning the LCCs of red, blue and green emission can be obtained. This strategy may open new perspectives for developing high-encapsulation-efficiency, oriented, and homogeneous solid-state lighting composite films in the application of optical sensors and devices. PMID:26641951

  15. Hierarchically-Porous Carbon Derived from a Large-Scale Iron-based Organometallic Complex for Versatile Energy Storage.

    Science.gov (United States)

    Fan, Chao-Ying; Li, Huan-Huan; Wang, Hai-Feng; Sun, Hai-Zhu; Wu, Xing-Long; Zhang, Jing-Ping

    2016-06-22

    Inspired by the preparation of the hierarchically-porous carbon (HPC) derived from metal organic frameworks (MOFs) for energy storage, in this work, a simple iron-based metal- organic complex (MOC), which was simpler and cheaper compared with the MOF, was selected to achieve versatile energy storage. The intertwined 1 D nanospindles and enriched-oxygen doping of the HPC was obtained after one-step carbonization of the MOC. When employed in lithium-ion batteries, the HPC exhibited reversible capacity of 778 mA h g(-1) after 60 cycles at 50 mA g(-1) . Moreover, the HPC maintained a capacity of 188 mA h g(-1) after 400 cycles at 100 mA g(-1) as the anode material in a sodium-ion battery. In addition, the HPC served as the cathode matrix for evaluation of a lithium-sulfur battery. The general preparation process of the HPC is commercial, which is responsible for the large-scale production for its practical application.

  16. Hierarchically-Porous Carbon Derived from a Large-Scale Iron-based Organometallic Complex for Versatile Energy Storage.

    Science.gov (United States)

    Fan, Chao-Ying; Li, Huan-Huan; Wang, Hai-Feng; Sun, Hai-Zhu; Wu, Xing-Long; Zhang, Jing-Ping

    2016-06-22

    Inspired by the preparation of the hierarchically-porous carbon (HPC) derived from metal organic frameworks (MOFs) for energy storage, in this work, a simple iron-based metal- organic complex (MOC), which was simpler and cheaper compared with the MOF, was selected to achieve versatile energy storage. The intertwined 1 D nanospindles and enriched-oxygen doping of the HPC was obtained after one-step carbonization of the MOC. When employed in lithium-ion batteries, the HPC exhibited reversible capacity of 778 mA h g(-1) after 60 cycles at 50 mA g(-1) . Moreover, the HPC maintained a capacity of 188 mA h g(-1) after 400 cycles at 100 mA g(-1) as the anode material in a sodium-ion battery. In addition, the HPC served as the cathode matrix for evaluation of a lithium-sulfur battery. The general preparation process of the HPC is commercial, which is responsible for the large-scale production for its practical application. PMID:27219476

  17. An interpenetrated pillared-layer MOF: Synthesis, structure, sorption and magnetic properties

    Energy Technology Data Exchange (ETDEWEB)

    Jia, Li-Na [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, College of Chemistry and Materials Science, Northwest University, Xi' an 710069 (China); Zhao, Yang [Research and Development Department, Zhejiang Quhua Fluorine Chemistry Co., Ltd., Zhejiang 324004 (China); Hou, Lei, E-mail: lhou2009@nwu.edu.cn [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, College of Chemistry and Materials Science, Northwest University, Xi' an 710069 (China); Cui, Lin; Wang, Hai-Hua; Wang, Yao-Yu [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, College of Chemistry and Materials Science, Northwest University, Xi' an 710069 (China)

    2014-02-15

    A new three-dimensional porous framework [Co{sub 2}(bpdc){sub 2}(H{sub 2}bpz)]∙2(DMF)·5(H{sub 2}O) (1) (H{sub 2}bpdc=4,4′-biphenyldicarboxylic acid, H{sub 2}bpz=3,3′,5,5′-tetramethyl-4,4′-bipyrazole) has been solvothermally synthesized by employing mixed H{sub 2}bpdc and H{sub 2}bpz ligands. 1 is a pillared-layer framework based on a binuclear paddle-wheel Co{sub 2}(O{sub 2}C-R){sub 4} cluster, and exhibits a 2-fold interpenetrated 6-connected pcu topology. H{sub 2}bpz bridges Co{sub 2}(O{sub 2}C-R){sub 4} clusters with an angular coordination configuration to form interesting left- and right-handed helical chains. 1 possesses a two-dimensional porous system decorated by uncoordinated pyrazole –NH groups of H{sub 2}bpz, leading to high adsorption selectivities for CO{sub 2} over N{sub 2} and H{sub 2}. In addition, the strong antiferromagnetic interactions between the Co{sup 2+} ions in cluster were observed. - Graphical abstract: A new pillared-layer porous framework has been constructed by paddle-wheel Co{sub 2}(O{sub 2}C-R){sub 4} cluster and H{sub 2}bpdc–H{sub 2}bpz mixed ligands, displaying adsorption selectivity and antiferromagnetic properties. Display Omitted - Highlights: • We present a new pillared-layer framework based on paddle-wheel Co{sub 2}(O{sub 2}C-R){sub 4} cluster. • The framework possesses a 2-fold interpenetrated pcu topology. • The framework displays adsorption selectivity and antiferromagnetic properties.

  18. Solid-State NMR Spectroscopy of Metal–Organic Framework Compounds (MOFs

    Directory of Open Access Journals (Sweden)

    Stefan Kaskel

    2012-11-01

    Full Text Available Nuclear Magnetic Resonance (NMR spectroscopy is a well-established method for the investigation of various types of porous materials. During the past decade, metal–organic frameworks have attracted increasing research interest. Solid-state NMR spectroscopy has rapidly evolved into an important tool for the study of the structure, dynamics and flexibility of these materials, as well as for the characterization of host–guest interactions with adsorbed species such as xenon, carbon dioxide, water, and many others. The present review introduces and highlights recent developments in this rapidly growing field.

  19. Application of a novel 2D cadmium(II)-MOF in the formation of a photo-switch with a substantial on-off ratio.

    Science.gov (United States)

    Roy, Sumit; Dey, Arka; Ray, Partha Pratim; Ortega-Castro, Joaquín; Frontera, Antonio; Chattopadhyay, Shouvik

    2015-08-21

    A novel thiocyanate bridged 2D MOF, [CdL(μ-1,3-SCN)2]n, [HL = 2-(2-(ethylamino)ethyliminomethyl)-6-ethoxyphenol] has been synthesized and characterized by X-ray crystallography. The band gap of the synthesized material in the solid state has been determined by experimental measurements and compared with the theoretical value obtained from DFT calculations. For the first time, the single crystal X-ray crystallography of a MOF has been reported along with its applicability in photosensitive devices. PMID:26176024

  20. Increase in Electrical Conductivity of MOF to Billion-Fold upon Filling the Nanochannels with Conducting Polymer.

    Science.gov (United States)

    Dhara, Barun; Nagarkar, Sanjog S; Kumar, Jitender; Kumar, Vikash; Jha, Plawan Kumar; Ghosh, Sujit K; Nair, Sunil; Ballav, Nirmalya

    2016-08-01

    Redox-active pyrrole (Py) monomers were intercalated into 1D nanochannels of [Cd(NDC)0.5(PCA)]·Gx (H2NDC = 2,6-napthalenedicarboxylic acid, HPCA = 4-pyridinecarboxylic acid, G = guest molecules) (1) - a fluorescent 3D MOF (λem = 385 nm). Subsequent activation of 1⊃Py upon immersing into iodine (I2) solution resulted in an increment of the bulk electrical conductivity by ∼9 orders of magnitude. The unusual increase in conductivity was attributed to the formation of highly oriented and conducting polypyrrole (PPy) chains inside 1D nanochannels and specific host-guest interaction in 1⊃PPy thereof. The Hall-effect measurements suggested 1⊃PPy to be an n-type semiconductor material with remarkably high-carrier density (η) of ∼1.5 × 10(17) cm(-3) and mobility (μ) of ∼8.15 cm(2) V(-1) s(-1). The fluorescence property of 1 was almost retained in 1⊃PPy with concomitant exciplex-type emission at higher wavelength (λem = 520 nm). The here-presented results on [MOF⊃Conducting Polymer] systems in general will serve as a prototype experiment toward rational design for the development of highly conductive yet fluorescent MOF-based materials for various optoelectronic applications. PMID:27404432

  1. Study on Reusable MOF Meta-modeling Framework%可复用MOF元建模框架的研究

    Institute of Scientific and Technical Information of China (English)

    兰庆国; 刘淑芬; 张欣佳

    2007-01-01

    在MDA场景下,元模型是实现平台无关模型和平台相关模型转换的核心.提出通过元层模型和模型层模型的Down-Up机制给出可复用的MOF元建模框架.元建模框架由MOF BootStrap模型自举,并且内置MOF Model,此框架可在任意多层元建模中复用.此外,给出了模型工程模型和模型迁移剪枝算法,并提出了采用模型工程统一对象空间实现模型实例复用的方法.此框架的研究对于指导具体建模工具的实现有重要意义.

  2. Increase in Electrical Conductivity of MOF to Billion-Fold upon Filling the Nanochannels with Conducting Polymer.

    Science.gov (United States)

    Dhara, Barun; Nagarkar, Sanjog S; Kumar, Jitender; Kumar, Vikash; Jha, Plawan Kumar; Ghosh, Sujit K; Nair, Sunil; Ballav, Nirmalya

    2016-08-01

    Redox-active pyrrole (Py) monomers were intercalated into 1D nanochannels of [Cd(NDC)0.5(PCA)]·Gx (H2NDC = 2,6-napthalenedicarboxylic acid, HPCA = 4-pyridinecarboxylic acid, G = guest molecules) (1) - a fluorescent 3D MOF (λem = 385 nm). Subsequent activation of 1⊃Py upon immersing into iodine (I2) solution resulted in an increment of the bulk electrical conductivity by ∼9 orders of magnitude. The unusual increase in conductivity was attributed to the formation of highly oriented and conducting polypyrrole (PPy) chains inside 1D nanochannels and specific host-guest interaction in 1⊃PPy thereof. The Hall-effect measurements suggested 1⊃PPy to be an n-type semiconductor material with remarkably high-carrier density (η) of ∼1.5 × 10(17) cm(-3) and mobility (μ) of ∼8.15 cm(2) V(-1) s(-1). The fluorescence property of 1 was almost retained in 1⊃PPy with concomitant exciplex-type emission at higher wavelength (λem = 520 nm). The here-presented results on [MOF⊃Conducting Polymer] systems in general will serve as a prototype experiment toward rational design for the development of highly conductive yet fluorescent MOF-based materials for various optoelectronic applications.

  3. Convection in porous media

    CERN Document Server

    Nield, Donald A

    1992-01-01

    This book provides a user-friendly introduction to the topic of convection in porous media The authors as- sume that the reader is familiar with the basic elements of fluid mechanics and heat transfer, but otherwise the book is self-contained The book will be useful both as a review (for reference) and as a tutorial work, suitable as a textbook in a graduate course or seminar The book brings into perspective the voluminous research that has been performed during the last two decades The field has recently exploded because of worldwide concern with issues such as energy self-sufficiency and pollution of the environment Areas of application include the insulation of buildings and equipment, energy storage and recovery, geothermal reservoirs, nuclear waste disposal, chemical reactor engineering, and the storage of heat-generating materials such as grain and coal Geophysical applications range from the flow of groundwater around hot intrusions to the stability of snow against avalanches

  4. Biogenic Cracks in Porous Rock

    Science.gov (United States)

    Hemmerle, A.; Hartung, J.; Hallatschek, O.; Goehring, L.; Herminghaus, S.

    2014-12-01

    Microorganisms growing on and inside porous rock may fracture it by various processes. Some of the mechanisms of biofouling and bioweathering are today identified and partially understood but most emphasis is on chemical weathering, while mechanical contributions have been neglected. However, as demonstrated by the perseverance of a seed germinating and cracking up a concrete block, the turgor pressure of living organisms can be very significant. Here, we present results of a systematic study of the effects of the mechanical forces of growing microbial populations on the weathering of porous media. We designed a model porous medium made of glass beads held together by polydimethylsiloxane (PDMS), a curable polymer. The rheological properties of the porous medium, whose shape and size are tunable, can be controlled by the ratio of crosslinker to base used in the PDMS (see Fig. 1). Glass and PDMS being inert to most chemicals, we are able to focus on the mechanical processes of biodeterioration, excluding any chemical weathering. Inspired by recent measurements of the high pressure (~0.5 Mpa) exerted by a growing population of yeasts trapped in a microfluidic device, we show that yeast cells can be cultured homogeneously within porous medium until saturation of the porous space. We investigate then the effects of such an inner pressure on the mechanical properties of the sample. Using the same model system, we study also the complex interplay between biofilms and porous media. We focus in particular on the effects of pore size on the penetration of the biofilm within the porous sample, and on the resulting deformations of the matrix, opening new perspectives into the understanding of life in complex geometry. Figure 1. Left : cell culture growing in a model porous medium. The white spheres represent the grains, bonds are displayed in grey, and microbes in green. Right: microscopy picture of glass beads linked by PDMS bridges, scale bar: 100 μm.

  5. Porous media geometry and transports

    CERN Document Server

    Adler, Pierre

    1992-01-01

    The goal of ""Porous Media: Geometry and Transports"" is to provide the basis of a rational and modern approach to porous media. This book emphasizes several geometrical structures (spatially periodic, fractal, and random to reconstructed) and the three major single-phase transports (diffusion, convection, and Taylor dispersion).""Porous Media"" serves various purposes. For students it introduces basic information on structure and transports. Engineers will find this book useful as a readily accessible assemblage of al the major experimental results pertaining to single-phase tr

  6. Extraction of Lanthanide and Actinide Ions from Aqueous Mixtures Using a Carboxylic Acid-Functionalized Porous Aromatic Framework.

    Science.gov (United States)

    Demir, Selvan; Brune, Nicholas K; Van Humbeck, Jeffrey F; Mason, Jarad A; Plakhova, Tatiana V; Wang, Shuao; Tian, Guoxin; Minasian, Stefan G; Tyliszczak, Tolek; Yaita, Tsuyoshi; Kobayashi, Tohru; Kalmykov, Stepan N; Shiwaku, Hideaki; Shuh, David K; Long, Jeffrey R

    2016-04-27

    Porous aromatic frameworks (PAFs) incorporating a high concentration of acid functional groups possess characteristics that are promising for use in separating lanthanide and actinide metal ions, as required in the treatment of radioactive waste. These materials have been shown to be indefinitely stable to concentrated acids and bases, potentially allowing for multiple adsorption/stripping cycles. Additionally, the PAFs combine exceptional features from MOFs and inorganic/activated carbons giving rise to tunable pore surfaces and maximum chemical stability. Herein, we present a study of the adsorption of selected metal ions, Sr(2+), Fe(3+), Nd(3+), and Am(3+), from aqueous solutions employing a carbon-based porous aromatic framework, BPP-7 (Berkeley Porous Polymer-7). This material displays high metal loading capacities together with excellent adsorption selectivity for neodymium over strontium based on Langmuir adsorption isotherms and ideal adsorbed solution theory (IAST) calculations. Based in part upon X-ray absorption spectroscopy studies, the stronger adsorption of neodymium is attributed to multiple metal ion and binding site interactions resulting from the densely functionalized and highly interpenetrated structure of BPP-7. Recyclability and combustibility experiments demonstrate that multiple adsorption/stripping cycles can be completed with minimal degradation of the polymer adsorption capacity. PMID:27163056

  7. Biocompatibility and osteogenic properties of porous tantalum

    OpenAIRE

    Wang, Qian; Zhang, Hui; LI, QIJIA; Ye,Lei; GAN, HONGQUAN; Liu, Yingjie; Wang, Hui; Wang, Zhiqiang

    2015-01-01

    Porous tantalum has been reported to be a promising material for use in bone tissue engineering. In the present study, the biocompatibility and osteogenic properties of porous tantalum were studied in vitro and in vivo. The morphology of porous tantalum was observed using scanning electron microscopy (SEM). Osteoblasts were cultured with porous tantalum, and cell morphology, adhesion and proliferation were investigated using optical microscopy and SEM. In addition, porous tantalum rods were i...

  8. Porous substrates filled with nanomaterials

    Science.gov (United States)

    Worsley, Marcus A.; Baumann, Theodore F.; Satcher, Jr., Joe H.; Stadermann, Michael

    2014-08-19

    A composition comprising: at least one porous carbon monolith, such as a carbon aerogel, comprising internal pores, and at least one nanomaterial, such as carbon nanotubes, disposed uniformly throughout the internal pores. The nanomaterial can be disposed in the middle of the monolith. In addition, a method for making a monolithic solid with both high surface area and good bulk electrical conductivity is provided. A porous substrate having a thickness of 100 microns or more and comprising macropores throughout its thickness is prepared. At least one catalyst is deposited inside the porous substrate. Subsequently, chemical vapor deposition is used to uniformly deposit a nanomaterial in the macropores throughout the thickness of the porous substrate. Applications include electrical energy storage, such as batteries and capacitors, and hydrogen storage.

  9. Quest for anionic MOF membranes: Continuous sod -ZMOF membrane with Co2 adsorption-driven selectivity

    KAUST Repository

    Almaythalony, Bassem

    2015-02-11

    We report the fabrication of the first continuous zeolite-like metal-organic framework (ZMOF) thin-film membrane. A pure phase sod-ZMOF, sodalite topology, membrane was grown and supported on a porous alumina substrate using a solvothermal crystallization method. The absence of pinhole defects in the film was confirmed and supported by the occurrence of quantifiable time-lags, for all studied gases, during constant volume/variable pressure permeation tests. For both pure and mixed gas feeds, the sod-ZMOF-1 membrane exhibits favorable permeation selectivity toward carbon dioxide over relevant industrial gases such as H2, N2, and CH4, and it is mainly governed by favorable CO2 adsorption.

  10. Highly selective adsorption of ethylene over ethane in a MOF featuring the combination of open metal site and π-complexation

    NARCIS (Netherlands)

    Y. Zhang; B. Li; R. Krishna; Z. Wu; D. Ma; Z. Shi; T. Pham; K. Forrest; B. Space; S. Ma

    2015-01-01

    The introduction of the combination of open metal site (OMS) and π-complexation into MOF has led to very high ethylene-ethane adsorption selectivity at 318 K, as illustrated in the context of MIL-101-Cr-SO3Ag. The interactions with ethylene from both OMS and π-complexation in MIL-101-Cr-SO3Ag have b

  11. The Cu-MOF-199/single-walled carbon nanotubes modified electrode for simultaneous determination of hydroquinone and catechol with extended linear ranges and lower detection limits.

    Science.gov (United States)

    Zhou, Jian; Li, Xi; Yang, Linlin; Yan, Songlin; Wang, Mengmeng; Cheng, Dan; Chen, Qi; Dong, Yulin; Liu, Peng; Cai, Weiquan; Zhang, Chaocan

    2015-10-29

    A novel electrochemical sensor based on Cu-MOF-199 [Cu-MOF-199 = Cu3(BTC)2 (BTC = 1,3,5-benzenetricarboxylicacid)] and SWCNTs (single-walled carbon nanotubes) was fabricated for the simultaneous determination of hydroquinone (HQ) and catechol (CT). The modification procedure was carried out through casting SWCNTs on the bare glassy carbon electrode (GCE) and followed by the electrodeposition of Cu-MOF-199 on the SWCNTs modified electrode. Cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM) were performed to characterize the electrochemical performance and surface characteristics of the as-prepared sensor. The composite electrode exhibited an excellent electrocatalytic activity with increased electrochemical signals towards the oxidation of HQ and CT, owing to the synergistic effect of SWCNTs and Cu-MOF-199. Under the optimized condition, the linear response range were from 0.1 to 1453 μmol L(-1) (RHQ = 0.9999) for HQ and 0.1-1150 μmol L(-1) (RCT = 0.9990) for CT. The detection limits for HQ and CT were as low as 0.08 and 0.1 μmol L(-1), respectively. Moreover, the modified electrode presented the good reproducibility and the excellent anti-interference performance. The analytical performance of the developed sensor for the simultaneous detection of HQ and CT had been evaluated in practical samples with satisfying results.

  12. Reversible flexible structural changes in multidimensional MOFs by guest molecules (I{sub 2}, NH{sub 3}) and thermal stimulation

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Yang; Li, Libo; Yang, Jiangfeng; Wang, Shuang; Li, Jinping, E-mail: Jpli211@hotmail.com

    2015-03-15

    Three metal–organic frameworks (MOFs), [Cu(INA){sub 2}], [Cu(INA){sub 2}I{sub 2}] and [Cu(INA){sub 2}(H{sub 2}O){sub 2}(NH{sub 3}){sub 2}], were synthesized with 3D, 2D, and 0D structures, respectively. Reversible flexible structural changes of these MOFs were reported. Through high temperature (60–100 °C) stimulation of I{sub 2} or ambient temperature stimulation of NH{sub 3}, [Cu(INA){sub 2}] (3D) converted to [Cu(INA){sub 2}I{sub 2}] (2D) and [Cu(INA){sub 2}(H{sub 2}O){sub 2}(NH{sub 3}){sub 2}] (0D); as the temperature increased to 150 °C, the MOFs changed back to their original form. In this way, this 3D MOF has potential application in the capture of I{sub 2} and NH{sub 3} from polluted water and air. XRD, TGA, SEM, NH{sub 3}-TPD, and the measurement of gas adsorption were used to describe the changes in processes regarding the structure, morphology, and properties. - Graphical abstract: Through I{sub 2}, NH{sub 3} molecules and thermal stimulation, the three MOFs can achieve reversible flexible structural changes. Different methods were used to prove the flexible reversible changes. - Highlights: • [Cu(INA){sub 2}] can flexible transform to [Cu(INA){sub 2}I{sub 2}] and [Cu(INA){sub 2}(H{sub 2}O){sub 2}(NH{sub 3}){sub 2}] by adsorbing I{sub 2} or NH{sub 3}. • The reversible flexible transformation related to material source, temperature and concentration. • Potential applications for the capture of I{sub 2} and NH{sub 3} from polluted water or air.

  13. Controllable synthesis of dual-MOFs nanostructures for pH-responsive artemisinin delivery, magnetic resonance and optical dual-model imaging-guided chemo/photothermal combinational cancer therapy.

    Science.gov (United States)

    Wang, Dongdong; Zhou, Jiajia; Chen, Ruhui; Shi, Ruohong; Zhao, Gaozheng; Xia, Guoliang; Li, Ren; Liu, Zhenbang; Tian, Jie; Wang, Huijuan; Guo, Zhen; Wang, Haibao; Chen, Qianwang

    2016-09-01

    Theranostic nanoagents which integrate diagnostic and therapeutic moieties into a single platform have attracted broad attention in cancer therapy, however the development of more effective and less toxic diagnostic and therapeutic interventions is still of great urgency. Herein, novel core-shell PB@MIL-100(Fe) dual metal-organic-frameworks (d-MOFs) nanoparticles are fabricated and their combined theranostic effects in vitro and in vivo are investigated. The d-MOFs nanoparticles can serve as a T1-T2 dual-modal magnetic resonance imaging (MRI) contrast and fluorescence optical imaging (FOI) agent due to the existence of inner PB MOFs and outer MIL-100(Fe) MOFs. The artemisinin (a traditional Chinese anticancer medicine) with a high loading content of 848.4 mg/g is released from the d-MOFs upon tumor cellular endocytosis due to the pH-responsive degradation of outer MOFs in low pH lysosomes of tumor cells. Furthermore, the inner PB MOFs can be utilized for photothermal therapy due to its strong absorbance in NIR region. Under the guidance by such dual-modal imaging, in vivo photothermal and chemotherapy is finally carried out, achieving effective tumor ablation in an animal tumor model. Furthermore, histological analysis revealed that the drug delivery system had no obvious effect on the major organs of mice due to the low toxicity of both d-MOFs and artemisinin. The distinctive multimodal imaging capability, excellent synergistic therapy effect through the combined chemo-photothermal therapy together with the low toxicity of both d-MOFs and artemisinin endow the theranostic nanoagent a promising next generation of nanomedicine for efficient and safe cancer therapy. PMID:27240160

  14. A Co3O4-embedded porous ZnO rhombic dodecahedron prepared using zeolitic imidazolate frameworks as precursors for CO2 photoreduction

    Science.gov (United States)

    Wang, Tao; Shi, Li; Tang, Jing; Malgras, Victor; Asahina, Shunsuke; Liu, Guigao; Zhang, Huabin; Meng, Xianguang; Chang, Kun; He, Jianping; Terasaki, Osamu; Yamauchi, Yusuke; Ye, Jinhua

    2016-03-01

    Metal-organic frameworks (MOFs) are attracting considerable attention for their use as both the precursor and the template to prepare metal oxides or carbon-based materials. For the first time in this paper, the core-shell ZIF-8@ZIF-67 crystals are thermally converted into porous ZnO@Co3O4 composites by combining a seed-mediated growth process with a two-step calcination. The designed porous ZnO@Co3O4 composites exhibited the highest photocatalytic activity with an excellent stability for the reduction of CO2 among the commonly reported composite photocatalysts. Their superior photocatalytic performance is demonstrated to be resulting from the unique porous structure of ZnO@Co3O4 and the co-catalytic function of Co3O4 which can effectively suppress the photocorrosion of ZnO.Metal-organic frameworks (MOFs) are attracting considerable attention for their use as both the precursor and the template to prepare metal oxides or carbon-based materials. For the first time in this paper, the core-shell ZIF-8@ZIF-67 crystals are thermally converted into porous ZnO@Co3O4 composites by combining a seed-mediated growth process with a two-step calcination. The designed porous ZnO@Co3O4 composites exhibited the highest photocatalytic activity with an excellent stability for the reduction of CO2 among the commonly reported composite photocatalysts. Their superior photocatalytic performance is demonstrated to be resulting from the unique porous structure of ZnO@Co3O4 and the co-catalytic function of Co3O4 which can effectively suppress the photocorrosion of ZnO. Electronic supplementary information (ESI) available: Additional TG and DTA curves, XRD patterns, SEM images, TEM images, N2 adsorption-desorption isotherms, X-ray photoelectron spectroscopy and GC-MS spectra of the samples. See DOI: 10.1039/c5nr08747c

  15. New Carbon-Based Porous Materials with Increased Heats of Adsorption for Hydrogen Storage

    Energy Technology Data Exchange (ETDEWEB)

    Snurr, Randall Q.; Hupp, Joseph T.; Kanatzidis, Mercouri G.; Nguyen, SonBinh T.

    2014-11-03

    . Only after modeling suggested record-breaking hydrogen uptake at 77 K did we proceed to synthesize, characterize, and test the material, ultimately yielding experimental results that agreed closely with predictions that were made before the material was synthesized. We also synthesized, characterized, and computationally simulated the behavior of two new materials displaying the highest experimental Brunauer−Emmett−Teller (BET) surface areas of any porous materials reported to date (∼7000 m2/g). Key to evacuating the initially solvent-filled materials without pore collapse, and thereby accessing the ultrahigh areas, was the use of a supercritical CO2 activation technique developed by our team. In our efforts to increase the hydrogen binding energy, we developed the first examples of “zwitterionic” metal-organic frameworks (MOFs). The two structures feature zwitterionic characteristics arising from N-heterocyclic azolium groups in the linkers and negatively charged Zn2(CO2)5 nodes. These groups interact strongly with the H2 quadrupole. High initial isosteric heats of adsorption for hydrogen were measured at low H2 loading. Simulations were used to determine the H2 binding sites, and results were compared with inelastic neutron scattering. In addition to MOFs, the project produced a variety of related materials known as porous organic frameworks (POFs), including robust catechol-functionalized POFs with tunable porosities and degrees of functionalization. Post-synthesis metalation was readily carried out with a wide range of metal precursors (CuII, MgII, and MnII salts and complexes), resulting in metalated POFs with enhanced heats of hydrogen adsorption compared to the starting nonmetalated materials. Isosteric heats of adsorption as high as 9.6 kJ/mol were observed, compared to typical values around 5 kJ/mol in unfunctionalized MOFs and POFs. Modeling played an important role throughout the project. For example, we used molecular simulations to determine that

  16. On strength of porous material

    DEFF Research Database (Denmark)

    Nielsen, Lauge Fuglsang

    1999-01-01

    quality without damaging or destroying the material or the building component considered. The efficiency of MOE-MOR relations for this purpose depends very much on the homogeneity of porous material considered. For building materials like wood and concrete of normal or lower quality with a number of......The question of non-destructive testing of porous materials has always been of interest for the engineering profession. A number of empirically based MOE-MOR relations between stiffness (Modulus Of Elasticity) and strength (Modulus OF Rupture) of materials have been established in order to control...... irregularities only scattered MOE-MOR relations (clouds) can be established from which no really results can be read.For homogeneously produced porous materials, however, like modern ceramics and high performance concretes MOE-MOR relations can be presented which are reliable. The present paper contributes to...

  17. Porous microsphere and its applications

    Directory of Open Access Journals (Sweden)

    Cai Y

    2013-03-01

    Full Text Available Yunpeng Cai,1,2* Yinghui Chen,3* Xiaoyun Hong,2 Zhenguo Liu,1 Weien Yuan2 1Department of Neurology, Xinhua Hospital affiliated to Shanghai Jiaotong University School of Medicine, 2School of Pharmacy, Shanghai JiaoTong University, 3Department of Neurology Jinshan Hospital, Fudan University, Shanghai, People's Republic of China *These authors contributed equally to this workAbstract: Porous microspheres have drawn great attention in the last two decades for their potential applications in many fields, such as carriers for drugs, absorption and desorption of substances, pulmonary drug delivery, and tissue regeneration. The application of porous microspheres has become a feasible way to address existing problems. In this essay, we give a brief introduction of the porous microsphere, its characteristics, preparation methods, applications, and a brief summary of existing problems and research tendencies.Keywords: pore, porosity, porogen, suspension polymerization, seed swelling, pulmonary drug delivery, tissue regeneration

  18. Formation of porous gas hydrates

    CERN Document Server

    Salamatin, Andrey N

    2015-01-01

    Gas hydrates grown at gas-ice interfaces are examined by electron microscopy and found to have a submicron porous texture. Permeability of the intervening hydrate layers provides the connection between the two counterparts (gas and water molecules) of the clathration reaction and makes further hydrate formation possible. The study is focused on phenomenological description of principal stages and rate-limiting processes that control the kinetics of the porous gas hydrate crystal growth from ice powders. Although the detailed physical mechanisms involved in the porous hydrate formation still are not fully understood, the initial stage of hydrate film spreading over the ice surface should be distinguished from the subsequent stage which is presumably limited by the clathration reaction at the ice-hydrate interface and develops after the ice grain coating is finished. The model reveals a time dependence of the reaction degree essentially different from that when the rate-limiting step of the hydrate formation at...

  19. Nonequilibrium Thermodynamics of Porous Electrodes

    CERN Document Server

    Ferguson, Todd R

    2012-01-01

    We review classical porous electrode theory and extend it to non-ideal active materials, including those capable of phase transformations. Using principles of non-equilibrium thermodynamics, we relate the cell voltage, ionic fluxes, and Faradaic charge-transfer kinetics to the variational electrochemical potentials of ions and electrons. The Butler-Volmer exchange current is consistently expressed in terms of the activities of the reduced, oxidized and transition states, and the activation overpotential is defined relative to the local Nernst potential. We also apply mathematical bounds on effective diffusivity to estimate porosity and tortuosity corrections. The theory is illustrated for a Li-ion battery with active solid particles described by a Cahn-Hilliard phase-field model. Depending on the applied current and porous electrode properties, the dynamics can be limited by electrolyte transport, solid diffusion and phase separation, or intercalation kinetics. In phase-separating porous electrodes, the model...

  20. Joining porous components to solid metal structures

    Science.gov (United States)

    Fortini, A.; Tulisiak, G.

    1972-01-01

    Process for joining porous metal material to solid metal structure without cracking or blockage of porous component is described. Procedures of electron beam welding and electroforming are discussed. Illustration of microstructure resulting from process is included.

  1. Construction and maintenace of porous asphalt

    OpenAIRE

    Kert, Gregor

    2012-01-01

    In improving traffic safety and reducing traffic noise road building experts from Slovenia and the world are faced with permeable surfaces - namely porous asphalt. There is hardly any water retention on road surfaces with the use of porous asphalt, what Slovenian engineers efficiently use on motorways where transverse profile changes its direction. Lately, porous asphalt is also being used for traffic noise reduction. However, porous road surface has some important disadvantages due to its...

  2. Hydrogen adsorption over Zeolite-like MOF materials modified by ion exchange

    Energy Technology Data Exchange (ETDEWEB)

    Calleja, G.; Botas, J.A.; Orcajo, M.G. [Department of Chemical and Energy Technology, ESCET, Universidad Rey Juan Carlos, C/Tulipan s/n, 28933 Mostoles, Madrid (Spain); Sanchez-Sanchez, M. [Instituto de Catalisis y Petroleoquimica, CSIC, C/Marie Curie 2, 28049 Madrid (Spain)

    2010-09-15

    Novel porous Zeolite-like metal-organic framework (ZMOF) materials with Rho and Sod topologies are promising adsorbents for hydrogen storage due to their high surface area and, more importantly, to their capacity of being ion-exchanged, potentially changing their affinity for hydrogen. In this work, we have successfully synthesized both Rho and SodZMOF materials, optimizing experimental conditions for scaling-up the procedure already published to produce grams of material. The resultant materials were alkaline-cation-exchanged, widely characterized and finally tested as hydrogen adsorbents. RhoZMOF is converted into an amorphous phase during some of the ion-exchange processes, whereas SodZMOF, whose ion-exchange capacity has not been investigated so far, always maintains its topology for any tested exchange cation and conditions. Additionally, thermogravimetric analyses and thermal treatments followed by in-situ powder X-ray diffraction analysis have evidenced a significantly higher thermal stability of both as-prepared and ion-exchanged SodZMOF materials in comparison to their Rho-structured homologues. Moreover, the thermal stability of the cation-exchanged ZMOF samples improves when methanol is the ion-exchange solvent rather than the reported ethanol-water mixture. Nitrogen and hydrogen adsorption isotherms at 77 K suggested that alkali-exchanged materials have lower affinity for hydrogen than the as-prepared samples compensated by imidazolium ion; however, due to the smaller size of Na{sup +} or Li{sup +} cations, their lower affinity is easily compensated by the inherent increase in surface area and pore volume as exchange degree increases. (author)

  3. Unusual Transformation from a Solvent-Stabilized 1D Coordination Polymer to a Metal-Organic Framework (MOF)-Like Cross-Linked 3D Coordination Polymer.

    Science.gov (United States)

    Lee, Seung-Chul; Choi, Eun-Young; Lee, Sang-Beom; Kim, Sang-Wook; Kwon, O-Pil

    2015-10-26

    An unusual 1D-to-3D transformation of a coordination polymer based on organic linkers containing highly polar push-pull π-conjugated side chains is reported. The coordination polymers are synthesized from zinc nitrate and an organic linker, namely, 2,5-bis{4-[1-(4-nitrophenyl)pyrrolidin-2-yl]butoxy}terephthalic acid, which possesses highly polar (4-nitrophenyl)pyrrolidine groups, with high dipole moments of about 7 D. The coordination polymers exhibit an unusual transformation from a soluble, solvent-stabilized 1D coordination polymer into an insoluble, metal-organic framework (MOF)-like 3D coordination polymer. The coordination polymer exhibits good film-forming ability, and the MOF-like films are insoluble in conventional organic solvents.

  4. The next chapter in MOF pillaring strategies: Trigonal heterofunctional ligands to access targeted high-connected three dimensional nets, isoreticular platforms

    KAUST Repository

    Eubank, Jarrod F.

    2011-11-09

    A new pillaring strategy, based on a ligand-to-axial approach that combines the two previous common techniques, axial-to-axial and ligand-to-ligand, and permits design, access, and construction of higher dimensional MOFs, is introduced and validated. Trigonal heterofunctional ligands, in this case isophthalic acid cores functionalized at the 5-position with N-donor (e.g., pyridyl- or triazolyl-type) moieties, are designed and utilized to pillar pretargeted two-dimensional layers (supermolecular building layers, SBLs). These SBLs, based on edge transitive Kagomé and square lattices, are cross-linked into predicted three-dimensional MOFs with tunable large cavities, resulting in isoreticular platforms. © 2011 American Chemical Society.

  5. Additively manufactured porous tantalum implants

    NARCIS (Netherlands)

    Wauthle, Ruben; Van Der Stok, Johan; Yavari, Saber Amin; Van Humbeeck, Jan; Kruth, Jean Pierre; Zadpoor, Amir Abbas; Weinans, Harrie; Mulier, Michiel; Schrooten, Jan

    2015-01-01

    The medical device industry's interest in open porous, metallic biomaterials has increased in response to additive manufacturing techniques enabling the production of complex shapes that cannot be produced with conventional techniques. Tantalum is an important metal for medical devices because of it

  6. Porous Materials - Structure and Properties

    DEFF Research Database (Denmark)

    Nielsen, Anders

    1997-01-01

    The paper presents some viewpoints on the description of the pore structure and the modelling of the properties of the porous building materials. Two examples are given , where it has been possible to connect the pore structure to the properties: Shrinkage of autoclaved aerated concrete and the p...... and the properties of lime mortar....

  7. From discrete molecule, to polymer, to MOF: mapping the coordination chemistry of Cd(II) using (113)Cd solid-state NMR.

    Science.gov (United States)

    Frost, Jamie M; Kobera, Libor; Pialat, Amélie; Zhang, Yixin; Southern, Scott A; Gabidullin, Bulat; Bryce, David L; Murugesu, Muralee

    2016-08-23

    Studies of three related Cd(II) systems (a discrete [Cd(II)2] unit, a one-dimensional [Cd(II)2]n coordination polymer and a Cd(II)-based MOF) all derived from the ligand 2,4,6-tris(2-pyrimidyl)-1,3,5-triazine, reveal an exceptionally rare example of (113)Cd-(113)Cd J coupling in the polymer that is detectable by solid-state NMR ((2)JCd-Cd = ∼65 Hz).

  8. Introduction of π-complexation into porous aromatic framework for highly selective adsorption of ethylene over ethane

    KAUST Repository

    Li, Baiyan

    2014-06-18

    In this work, we demonstrate for the first time the introduction of π-complexation into a porous aromatic framework (PAF), affording significant increase in ethylene uptake capacity, as illustrated in the context of Ag(I) ion functionalized PAF-1, PAF-1-SO3Ag. IAST calculations using single-component-isotherm data and an equimolar ethylene/ethane ratio at 296 K reveal that PAF-1-SO3Ag shows exceptionally high ethylene/ethane adsorption selectivity (Sads: 27 to 125), far surpassing benchmark zeolite and any other MOF reported in literature. The formation of π-complexation between ethylene molecules and Ag(I) ions in PAF-1-SO 3Ag has been evidenced by the high isosteric heats of adsorption of C2H4 and also proved by in situ IR spectroscopy studies. Transient breakthrough experiments, supported by simulations, indicate the feasibility of PAF-1-SO3Ag for producing 99.95%+ pure C 2H4 in a Pressure Swing Adsorption operation. Our work herein thus suggests a new perspective to functionalizing PAFs and other types of advanced porous materials for highly selective adsorption of ethylene over ethane. © 2014 American Chemical Society.

  9. Structure and magnetism of a porous three-dimensional metal-organic framework based on planar tetranuclear copper(Ⅱ) cluster units

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    A porous three-dimensional copper(Ⅱ) metal-organic framework (MOF) {[Cu2(tci)(OH)(pip)0.5(H2O)]·6H2O}n (1) [tci = tris (2-carboxyethyl)isocyanurate, pip = piperazine] has been generated under hydrothermal conditions at 120 °C. Single crystal X-ray diffraction reveals that the polymer exhibits a novel three-dimensional framework based on planar tetranuclear copper(Ⅱ) cluster units. The variable temperature magnetic susceptibility data in the range 2-280 K show antiferromagnetic spin-spin coupling in the tetranuclear unit in complex 1. A theoretical fitting of the magnetic data gives J values of -31.3 cm-1, -30.8 cm-1, and 13.5 cm-1.

  10. Symmetry-Guided Synthesis of Highly Porous Metal-Organic Frameworks with Fluorite Topology

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, MW; Chen, YP; Bosch, M; Gentle, T; Wang, KC; Feng, DW; Wang, ZYU; Zhou, HC

    2013-11-11

    Two stable, non-interpenetrated MOFs, PCN-521 and PCN-523, were synthesized by a symmetry-guided strategy. Augmentation of the 4-connected nodes in the fluorite structure with a rigid tetrahedral ligand and substitution of the 8-connected nodes by the Zr/Hf clusters yielded MOFs with large octahedral interstitial cavities. They are the first examples of Zr/Hf MOFs with tetrahedral linkers. PCN-521 has the largest BET surface area (3411 m(2) g(-1)), pore size (20.5 x 20.5 x 37.4 angstrom) and void volume (78.5%) of MOFs formed from tetrahedral ligands. This work not only demonstrates a successful implementation of rational design of MOFs with desired topology, but also provides a systematic way of constructing non-interpenetrated MOFs with high porosity.

  11. Crystallization of copper(II) sulfate based minerals and MOF from solution: Chemical insights into the supramolecular interactions

    Indian Academy of Sciences (India)

    M Singh; D Kumar; J Thomas; A Ramanan

    2010-09-01

    Crystallization of solids, molecular or non-molecular from solution is a supramolecular reaction. Nucleation of a lattice structure at supersaturation can be conceived to result from a critical nucleus, a high energy intermediate (supramolecular transition state). Conceptualization of a structure for the critical nucleus in terms of aggregation of tectons through non-covalent interactions provides chemical insights into the architecture of a solid. The retrosynthetic analysis of copper-based minerals and materials offers an elegant description for the crystal packing. It addresses the influence of the geometry, functionality and reactivity of copper tecton(s) in directing a specific supramolecular aggregation. The mechanistic approach provides guiding principles to chemists to account for the experimentally crystallized solids and a platform to practice structure-synthesis correlation. Rationalization of the same composition with different atomic arrangements (polymorphs), compositional variation leading to different pseudopolymorphs, degree of hydration (anhydrous to hydrated), water clusters, role of solvent, etc. can all be justified on molecular basis. Also, the method gives predictive components including directions to synthesize new solids. In a nutshell, the paper is an attempt to generalize the crystallization of inorganic solids from solution by recognizing supramolecular interactions between metal tectons and gain insights for designing new MOF.

  12. Colloidal Photoluminescent Amorphous Porous Silicon, Methods Of Making Colloidal Photoluminescent Amorphous Porous Silicon, And Methods Of Using Colloidal Photoluminescent Amorphous Porous Silicon

    KAUST Repository

    Chaieb, Sahraoui

    2015-04-09

    Embodiments of the present disclosure provide for a colloidal photoluminescent amorphous porous silicon particle suspension, methods of making a colloidal photoluminescent amorphous porous silicon particle suspension, methods of using a colloidal photoluminescent amorphous porous silicon particle suspension, and the like.

  13. Giant Negative Area Compressibility Tunable in a Soft Porous Framework Material.

    Science.gov (United States)

    Cai, Weizhao; Gładysiak, Andrzej; Anioła, Michalina; Smith, Vincent J; Barbour, Leonard J; Katrusiak, Andrzej

    2015-07-29

    A soft porous material [Zn(L)2(OH)2]n·Guest (where L is 4-(1H-naphtho[2,3-d]imidazol-1-yl)benzoate, and Guest is water or methanol) exhibits the strongest ever observed negative area compressibility (NAC), an extremely rare property, as at hydrostatic pressure most materials shrink in all directions and few expand in one direction. This is the first NAC reported in metal-organic frameworks (MOFs), and its magnitude, clearly visible and by far the highest of all known materials, can be reversibly tuned by exchanging guests adsorbed from hydrostatic fluids. This counterintuitive strong NAC of [Zn(L)2(OH)2]n·Guest arises from the interplay of flexible [-Zn-O(H)-]n helices with layers of [-Zn-L-]4 quadrangular puckered rings comprising large channel voids. The compression of helices and flattening of puckered rings combine to give a giant piezo-mechanical response, applicable in ultrasensitive sensors and actuators. The extrinsic NAC response to different hydrostatic fluids is due to varied host-guest interactions affecting the mechanical strain within the range permitted by exceptionally high flexibility of the framework. PMID:25945394

  14. Moisture Sorption in Porous Materials

    DEFF Research Database (Denmark)

    Nielsen, Lauge Fuglsang

    2007-01-01

    Abstract: Information on pore geometry is very important in any study of the mechanical and physical behavior of porous materials. Unfortunately pores are not very accessible for direct measurements. Indirect methods have to be used which involve impregnation (sorption) experiments from which...... physical parameters, the so-called BET-parameters: The heat property factor, C, and the pore surface, SBET (derived from the so-called uni-molecular moisture content uBET). A software ‘SORP07’ has been developed to handle any calculations made in the paper. For readers who have a special interest...... in the subject considered this software is available on request to the author. Keywords: Porous materials, moisture, adsorption, desorption, BET-parameters....

  15. Scattering characteristics from porous silicon

    Directory of Open Access Journals (Sweden)

    R. Sabet-Dariani

    2000-12-01

    Full Text Available   Porous silicon (PS layers come into existance as a result of electrochemical anodization on silicon. Although a great deal of research has been done on the formation and optical properties of this material, the exact mechanism involved is not well-understood yet.   In this article, first, the optical properties of silicon and porous silicon are described. Then, previous research and the proposed models about reflection from PS and the origin of its photoluminescence are reveiwed. The reflecting and scattering, absorption and transmission of light from this material, are then investigated. These experiments include,different methods of PS sample preparation their photoluminescence, reflecting and scattering of light determining different characteristics with respect to Si bulk.

  16. Porous microsphere and its applications

    OpenAIRE

    Cai Y; Chen Y; Hong X; Liu Z; Yuan W

    2013-01-01

    Yunpeng Cai,1,2* Yinghui Chen,3* Xiaoyun Hong,2 Zhenguo Liu,1 Weien Yuan2 1Department of Neurology, Xinhua Hospital affiliated to Shanghai Jiaotong University School of Medicine, 2School of Pharmacy, Shanghai JiaoTong University, 3Department of Neurology Jinshan Hospital, Fudan University, Shanghai, People's Republic of China *These authors contributed equally to this workAbstract: Porous microspheres have drawn great attention in the last two decades for their potential applications ...

  17. Porous squeeze-film flow

    KAUST Repository

    Knox, D. J.

    2013-11-14

    © 2013 © The authors 2013. Published by Oxford University Press on behalf of the Institute of Mathematics and its Applications. All rights reserved. The squeeze-film flow of a thin layer of Newtonian fluid filling the gap between a flat impermeable surface moving under a prescribed constant load and a flat thin porous bed coating a stationary flat impermeable surface is considered. Unlike in the classical case of an impermeable bed, in which an infinite time is required for the two surfaces to touch, for a porous bed contact occurs in a finite contact time. Using a lubrication approximation, an implicit expression for the fluid layer thickness and an explicit expression for the contact time are obtained and analysed. In addition, the fluid particle paths are calculated, and the penetration depths of fluid particles into the porous bed are determined. In particular, the behaviour in the asymptotic limit of small permeability, in which the contact time is large but finite, is investigated. Finally, the results are interpreted in the context of lubrication in the human knee joint, and some conclusions are drawn about the contact time of the cartilage-coated femoral condyles and tibial plateau and the penetration of nutrients into the cartilage.

  18. Resurgence flows in porous media

    Science.gov (United States)

    Adler, Pierre; Mityushev, Vladimir

    2010-05-01

    Porous media are generally described by the Darcy equation when the length scales are sufficiently large with respect to the pore scale. This approach is also applicable when the media are heterogeneous, i.e., when permeability varies with space which is the most common case. In addition, real media are very often fractured; for a long time, this complex physical problem has been schematized by the double porosity model devised by Barenblatt. More recently, these fractured media have been addressed with a detailed description of the fractures and of their hydrodynamic interaction with the surrounding porous medium. This approach will be briefly summarized and the main recent progress surveyed (2). There is another situation which occurs frequently in underground studies. One well is connected to a distant well while it is not connected to closer wells. Such a situation can only be understood if there is a direct link between the two connected wells and if this link has little if any hydrodynamic interaction with the porous medium that it crosses. This link can be a fracture or more likely a set of fractures. This phenomenon is called resurgence because of the obvious analogy with rivers which suddenly disappear underground and go out at the ground surface again. Similar ideas have already been developed in other fields. In Physics, random networks limited to nearest neighbors have been recently extended to small world models where distant vertices can be related directly by a link. The electrical testing of porous media by electrical probes located at the walls (electrical tomography) has been used frequently in Geophysics since it is a non-invasive technique; this classical technique corresponds exactly to the situation addressed here from a different perspective. Media with resurgences consist of a double structure (3). The first one which is continuous is described by Darcy law as usual. The second one models the resurgences by capillaries with impermeable walls

  19. Dynamics of H2 adsorbed in porous materials as revealed by computational analysis of inelastic neutron scattering spectra.

    Science.gov (United States)

    Pham, Tony; Forrest, Katherine A; Space, Brian; Eckert, Juergen

    2016-06-29

    The inelastic scattering of neutrons from adsorbed H2 is an effective and highly sensitive method for obtaining molecular level information on the type and nature of H2 binding sites in porous materials. While these inelastic neutron scattering (INS) spectra of the hindered rotational and translational excitations on the adsorbed H2 contain a significant amount of information, much of this can only be reliably extracted by means of a detailed analysis of the spectra through the utilization of models and theoretical calculations. For instance, the rotational tunneling transitions observed in the INS spectra can be related to a value for the barrier to rotation for the adsorbed H2 with the use of a simple phenomenological model. Since such an analysis is dependent on the model, it is far more desirable to use theoretical methods to compute a potential energy surface (PES), from which the rotational barriers for H2 adsorbed at a particular site can be determined. Rotational energy levels and transitions for the hindered rotor can be obtained by quantum dynamics calculations and compared directly with experiment with an accuracy subject only to the quality of the theoretical PES. In this paper, we review some of the quantum and classical mechanical calculations that have been performed on H2 adsorbed in various porous materials, such as clathrate hydrates, zeolites, and metal-organic frameworks (MOFs). The principal aims of these calculations have been the interpretation of the INS spectra for adsorbed H2 along with the extraction of atomic level details of its interaction with the host. We describe calculations of the PES used for two-dimensional quantum rotation as well as rigorous five-dimensional quantum coupled translation-rotation dynamics, and demonstrate that the combination of INS measurements and computational modeling can provide important and detailed insights into the molecular mechanism of H2 adsorption in porous materials. PMID:27160665

  20. Propagation of waves in porous media

    OpenAIRE

    Çorapçıoplu, M. Yavuz; Tuncay, Kağan

    1996-01-01

    Wave propagation in porous media is of interest in various diversified areas of science and engineering. The theory of the phenomenon has been studied extensively in soil mechanics, seismology, acoustics, earthquake engineering, ocean engineering, geophysics, and many other disciplines. This review presents a general survey of the literature within the context of porous media mechanics. Following a review of the Biot's theory of wave propagation in linear, elastic, fluid saturated porous medi...

  1. Porous media heat transfer for injection molding

    Energy Technology Data Exchange (ETDEWEB)

    Beer, Neil Reginald

    2016-05-31

    The cooling of injection molded plastic is targeted. Coolant flows into a porous medium disposed within an injection molding component via a porous medium inlet. The porous medium is thermally coupled to a mold cavity configured to receive injected liquid plastic. The porous medium beneficially allows for an increased rate of heat transfer from the injected liquid plastic to the coolant and provides additional structural support over a hollow cooling well. When the temperature of the injected liquid plastic falls below a solidifying temperature threshold, the molded component is ejected and collected.

  2. Scaling effect of breakthroughcharacter in porous media

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Breakthrough phenomenon during fluids percolating through wet saturated porous layer is widely met in the study of heat and mass transfer in porous media. Breakthrough pressure (BP) is a characteristic pressure that indicates the intrinsic properties of seepage within porous media. Measuring results of BP for saturated narrow-sieved sand are reported here. The curve of BP varying with the height of porous layer was obtained. Experiment and analysis indicate that BP is independent of the height of particle packed layer if thick enough; however, when the height is less than a certain critical value, BP dimims hes with the decrease of the height according to a universal scaling law.

  3. A fine-tuned fluorinated MOF addresses the needs for trace CO2 removal and air capture using physisorption.

    KAUST Repository

    Bhatt, Prashant M.

    2016-07-08

    The development of functional solid-state materials for carbon capture at low carbon dioxide (CO2) concentrations, from con-fined spaces (<0.5 %) and particularly from air (400 ppm), is of prime importance with respect to energy and environment sustainability. Herein, we report the deliberate construction of a hydrolytically stable fluorinated metal-organic framework (MOF), NbOFFIVE-1-Ni, with the proper pore system (size, shape and functionality), ideal for efficient and effective traces carbon dioxide removal. Markedly, the CO2-selective NbOFFIVE-1-Ni exhibits the highest CO2 gravimetric and volumetric uptake (ca. 1.3 mmol/g and 51.4 cm3.cm-3) for physical adsorbents at 400 ppm CO2 and 298 K. Practically, the NbOFFIVE-1-Ni affords the complete CO2 desorption at 328 K under vacuum with an associated moderate energy input of 54 kJ/mol, typical for the full CO2 desorption in reference physical adsorbents but considerably lower than the conventional chemical sorbents. Noticeably, the contracted square-like channels, affording the close proximity of the fluorine centers, permitted the enhancement of the CO2-framework interactions and subsequently the attainment of an unprecedented CO2-selectivity at very low CO2 concentrations. The precise localization of the adsorbed CO2 at the vicinity of the periodically aligned fluorine centers, promoting the selective adsorption of CO2, is evidenced by the single-crystal X-ray diffraction study on the NbOFFIVE-1-Ni hosting CO2 molecules. Cyclic CO2/N2 mixed-gas column breakthrough experiments under dry and humid conditions corroborate the excellent CO2-selectivity under practical carbon capture conditions. Pertinently, the no-table hydrolytic stability positions the NbOFFIVE-1-Ni as the new benchmark adsorbent for direct air capture and CO2 removal from confined spaces.

  4. Thermodynamic Study of CO2 Sorption by Polymorphic Microporous MOFs with Open Zn(II) Coordination Sites.

    Science.gov (United States)

    Ahrenholtz, Spencer R; Landaverde-Alvarado, Carlos; Whiting, Macauley; Lin, Shaoyang; Slebodnick, Carla; Marand, Eva; Morris, Amanda J

    2015-05-01

    Two Zn-based metal organic frameworks have been prepared solvothermally, and their selectivity for CO2 adsorption was investigated. In both frameworks, the inorganic structural building unit is composed of Zn(II) bridged by the 2-carboxylate or 5-carboxylate pendants of 2,5-pyridine dicarboxylate (pydc) to form a 1D zigzag chain. The zigzag chains are linked by the bridging 2,5-carboxylates across the Zn ions to form 3D networks with formulas of Zn4(pydc)4(DMF)2·3DMF (1) and Zn2(pydc)2(DEF) (2). The framework (1) contains coordinated DMF as well as DMF solvates (DMF = N,N-dimethylformamide), while (2) contains coordinated DEF (DEF = N,N-diethylformamide). (1) displays a reversible type-I sorption isotherm for CO2 and N2 with BET surface areas of 196 and 319 m(2)/g, respectively. At low pressures, CO2 and N2 isotherms for (2) were not able to reach saturation, indicative of pore sizes too small for the gas molecules to penetrate. A solvent exchange to give (2)-MeOH allowed for increased CO2 and N2 adsorption onto the MOF surface with BET surface areas of 41 and 39 m(2)/g, respectively. The binding of CO2 into the framework of (1) was found to be exothermic with a zero coverage heat of adsorption, Qst(0), of −27.7 kJ/mol. The Qst(0) of (2) and (2)-MeOH were found to be −3 and −41 kJ/mol, respectively. The CO2/N2 selectivity for (1), calculated from the estimated KH at 296 K, was found to be 42. At pressures relevant to postcombustion capture, the selectivity was 14. The thermodynamic data are consistent with a mechanism of adsorption that involves CO2 binding to the unsaturated Zn(II) metal centers present in the crystal structures. PMID:25898142

  5. Ordered and disordered porous materials for nanofiltration application

    NARCIS (Netherlands)

    Chowdhury, Sankhanilay Roy

    2005-01-01

    This Ph.D. dissertation elaborates on the use of porous materials in fluid separation technology. Two different types of porous materials, namely surfactant templated silica and alumina have been used to prepare flat plate geometry porous membranes.

  6. Magnetism in a number of Metal Organic Frameworks (MOFs) with 1D and 3D characteristics: An experimental and analytical study

    Science.gov (United States)

    Hamida, Youcef

    Metal Organic Frameworks (MOFs) exhibit many excellent physical properties including magnetic properties for potential applications in devices. More importantly for the subject of this thesis, MOFs are ideal for the realization of low dimensional magnetism because of the large selection of ligands connecting magnetic centers in making the framework. The materials studied in this thesis include ten magnetic MOFs of the form M(L1)(L2) [M = Cu, Ni, Co, Fe, Mn; L1 = NDC, bpdc, BDC, BODC, N3; L2 = DMF, H2O, TED, bpy]. Polycrystalline powder samples as well as single crystal samples were synthesized. Their crystal structures were determined, and their magnetic and thermodynamic properties were measured and analyzed. Eight of these materials were characterized as 1D magnets and two as 3D magnets. In the 1D case it is found that above Tm [the temperature at which the magnetic susceptibility chi(T) has a peak] the magnetic behavior of MOFs (S ≥ 1) can be well described with the Classical Fisher Model (CFM). Near and below TC the spins take a more definite orientation than allowed for in the CFM and hence the Ising Model (IM) was used for fitting. Both CFM and IM yield fairly consistent intrachain couplings ( J) when applied in their appropriate temperature region. To estimate the interchain exchange (J'), the susceptibility for a magnetic chain in the mean field of neighboring chains is used. In all cases, as expected, the ratio of J to J' was less than 10%. The special case of Cu(N3)2bpy ( S = ½) was analyzed with the spin ½ IM. Although the specific heat data (Ctotal) for most of the 1D MOFs showed no clear phase transition, a low temperature fit to the electron-phonon specific heats yielded apparent heavy fermion-like gamma values on the order of several hundred mJ/mol K2. The lattice specific heat (Clattice) was estimated using a Debye-Einstein hybrid model. Subtracting Clattice from Ctotal, magnetic specific heat ( CM) with a broad peak characteristic of low

  7. Salt crystallisation at the surface of a heterogeneous porous medium

    OpenAIRE

    Veran-Tissoires, Stéphanie; Marcoux, Manuel; Prat, Marc

    2012-01-01

    International audience; Evaporation of saline solutions from a porous medium often leads to the precipitation of salt at the surface of the porous medium. It is commonly observed that the crystallized salt does not form everywhere at the porous medium surface but only at some specific locations. To explain this phenomenon, we consider efflorescence formation at the surface of a saturated heterogeneous porous column (finer porous medium in coarse porous medium background) in the wicking situat...

  8. ZnO/porous-Si and TiO{sub 2}/porous-Si nanocomposite nanopillars

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Dong, E-mail: dong.wang@tu-ilmenau.de; Yan, Yong; Schaaf, Peter [Chair Materials for Electronics, Institute of Materials Engineering and Institute of Micro- and Nanotechnologies MacroNano, TU Ilmenau, Gustav-Kirchhoff-Str. 5, 98693 Ilmenau (Germany); Sharp, Thomas [Oxford Instruments Plasma Technology Ltd., Yatton, Bristol BS49 4AP (United Kingdom); Schönherr, Sven; Ronning, Carsten [Institute for Solid State Physics, Friedrich Schiller University Jena, Max-Wien-Platz 1, 07743 Jena (Germany); Ji, Ran [SUSS MicroTec Lithography GmbH, Schleissheimer Str. 90, 85748 Garching (Germany)

    2015-01-01

    Porous Si nanopillar arrays are used as templates for atomic layer deposition of ZnO and TiO{sub 2}, and thus, ZnO/porous-Si and TiO{sub 2}/porous-Si nanocomposite nanopillars are fabricated. The diffusion of the precursor molecules into the inside of the porous structure occurs via Knudsen diffusion and is strongly limited by the small pore size. The luminescence of the ZnO/porous-Si nanocomposite nanopillars is also investigated, and the optical emission can be changed and even quenched after a strong plasma treatment. Such nanocomposite nanopillars are interesting for photocatalysis and sensors.

  9. Voltammetry at porous electrodes: A theoretical study

    OpenAIRE

    Barnes, Edward O; Chena, Xiaojun; Li, Peilin; Compton, Richard G.

    2014-01-01

    Theory is presented to simulate both chronoamperometry and cyclic voltammetry at porous electrodes fabricated by means of electro-deposition around spherical templates. A theoretical method to extract heterogeneous rate constants for quasireversible and irreversible systems is proposed by the approximation of decoupling of the diffusion within the porous electrode and of bulk diffusion to the electrode surface.

  10. Development in applications of porous metals

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Applications of porous metal materials are reviewed so far. These applications deal with filtration and separa tion, energy absorption, electrode matrix, fluid distribution and control, heat exchangers, reaction materials, construc tional materials, electromagnetic shielding, biomaterials and so on. All these are expected to promote the improvement of the property and structure for porous metals.

  11. A positron moderator using porous metal

    Institute of Scientific and Technical Information of China (English)

    WANG Bao-Yi; YU Run-Sheng; ZHAO Fa-Ru; MA Chuang-Xin; ZHANG Tian-Bao; WEI Long

    2004-01-01

    Two types of porous metal moderators (i.e. porous nickel layer and multi-wire tungsten layer) are proposed and tested on a slow positron beam line. A moderation efficiency of about 2×10-4 has been achieved, which is higher than that for W vane geometry moderator by a factor of 4.

  12. NMR of porous Bio-systems

    NARCIS (Netherlands)

    Snaar, E.J.M.

    2002-01-01

    The structure and dynamics of water diffusion and -transport at a microscale in heterogeneous porous media have been investigated using various 1H NMR techniques. In particular in biological porous media the dynamics are usually very complex since it is intimately related to th

  13. Post-Synthesis Functionalization of Porous Organic Polymers for CO2 Capture

    KAUST Repository

    Al Otaibi, Mona S.

    2014-07-01

    Solid porous materials are network materials that contain space void. Porous Organic Polymers (POPs) are porous materials, which are constructed from organic building blocks and exhibit large surface area with low densities. Due to these characteristics, POPs have attracted attentions because of their potential use in application such as gas storage and chemical separation. This thesis presents a study of the synthesis of novel POP being a network based on 2,5- dibromobenzaldehyde and 1,3,5-triethynylbenzene linked together via Sonogashira- Hagihara (SH) coupling. This network showed a relatively good surface area of 770 m2/g and total pore volume of 0.59 cc/g. In addition, it proved to be chemically and thermally stable, maintaining the thermal stability up to 350oC. In addition to synthesize novel aldehyde-POP network, it was also possible to post synthetically modify a network via one-step post synthetic functionalization by amine. Ethelynediamine (EDA), Diethylenetriamine (DETA), and Tris(2-aminoethyl)amine (Tris-amine) are three different amines used for aldehyde-POP functionalization. The produced networks were aminated via different amine species substitution the aldehyde group present within the network. Modification to these networks resulted in a decrease in surface area from 770 m2.g-1 to 333 m2.g-1, 162 m2.g-1, and 211 m2.g-1 in respective to EDA, DETA, and Tris-amine. Although the surface areas were decreased, the CO2 adsorption was enhanced as evidenced by the increase of Qst (i.e., from 25 to 45 kJ.mol-1 for DETA at low coverage). Our findings are expected to strengthen existing research areas of the influence of different type of amines (e.g aromatic amine) on CO2 adsorption. Although amine grafting has been studied in other systems (e.g., PAFs and MOFs), we are the first to reported amine functionalized POPs using a novel one-step amine grafting PSM procedure. Future research might extend to study the interaction between CO2 and amine species under

  14. Preparation and characterization of porous magnesium materials

    Institute of Scientific and Technical Information of China (English)

    LIU Xi-qin; LIU Zi-li; ZHANG Xiao-hong; FENG Jun-dong; YU Ta-xi

    2006-01-01

    The proper spacer material and the preparation technology for biological compatible porous magnesium materials were explored by the powder metallurgy method, and microstructures, porosity and mechanical properties of sintered porous magnesium were investigated. The results show that compared with spacer materials of NH4CO3, NH3Cl and carbamide, NH4CO3 is the best one for preparation of sintered porous magnesium, and the worst one is NH3Cl. The isolated blind pores are formed mainly by the particle interval of the magnesium powders. Adding spacer material favors the formation of open pores, while has little contribution to the formation of blind pores. The overall porosity and porosity of open pore of the sintered porous magnesium increase with the increase of added spacer material, while decrease with the increase of the molding stress. The mechanical properties of sintered porous magnesium increase with decreasing addition of spacer material and increasing molding stress.

  15. Anisotropic elastic properties of flexible metal-organic frameworks: how soft are soft porous crystals?

    Science.gov (United States)

    Ortiz, Aurélie U; Boutin, Anne; Fuchs, Alain H; Coudert, François-Xavier

    2012-11-01

    We performed ab initio calculations of the elastic constants of five flexible metal-organic frameworks (MOFs): MIL-53(Al), MIL-53(Ga), MIL-47, and the square and lozenge structures of DMOF-1. Tensorial analysis of the elastic constants reveals a highly anisotropic elastic behavior, some deformation directions exhibiting very low Young's modulus and shear modulus. This anisotropy can reach a 400:1 ratio between the most rigid and weakest directions, in stark contrast to the case of nonflexible MOFs such as MOF-5 and ZIF-8. In addition, we show that flexible MOFs can display extremely large negative linear compressibility. These results uncover the microscopic roots of stimuli-induced structural transitions in flexible MOFs, by linking the local elastic behavior of the material and its multistability. PMID:23215398

  16. Direct calorimetric measurement of enthalpy of adsorption of carbon dioxide on CD-MOF-2, a green metal-organic framework.

    Science.gov (United States)

    Wu, Di; Gassensmith, Jeremiah J; Gouvêa, Douglas; Ushakov, Sergey; Stoddart, J Fraser; Navrotsky, Alexandra

    2013-05-01

    The enthalpy of adsorption of CO2 on an environmentally friendly metal-organic framework, CD-MOF-2, has been determined directly for the first time using adsorption calorimetry at 25 °C. This calorimetric methodology provides a much more accurate and model-independent measurement of adsorption enthalpy than that obtained by calculation from the adsorption isotherms, especially for systems showing complex and strongly exothermic adsorption behavior. The differential enthalpy of CO2 adsorption shows enthalpy values in line with chemisorption behavior. At near-zero coverage, an irreversible binding event with an enthalpy of -113.5 kJ/mol CO2 is observed, which is followed by a reversible -65.4 kJ/mol binding event. These enthalpies are assigned to adsorption on more and less reactive hydroxyl groups, respectively. Further, a second plateau shows an enthalpy of -40.1 kJ/mol and is indicative of physisorbed CO2. The calorimetric data confirm the presence of at least two energetically distinct binding sites for chemisorbed CO2 on CD-MOF-2.

  17. Metabolism and nutritional support during MOF%多脏器功能衰竭的代谢与营养支持

    Institute of Scientific and Technical Information of China (English)

    M.Adolph

    2001-01-01

    The problems of inflammation and infection leading to organ dysfunction and failure continue to be the major concerns after injury and operations and with the intensive care for many diseases and problems.When systemic inflammatory response syndrome (SIRS) goes to multiple organ dysfunction syndrome (MODS) and multiple organ failure (MOF),the mortality ecomes high,ranging from 30-80% depending on the number of failed organs.In MOF or MODS respiratory failure develops with the need for ventilaroty support,accompanied by circulatory instability with depression of cardiac output and a decrease in peripheral resistance,depression of the immune system,coagulation defects,gastrointestinal problems,a rising bilirubin denoting hepatic dysfunction and central nervous depression.The elevation in whole body protein turnover after sepsis and trauma usually is accompanied by an increase in metabolic rate Hepatic output of acute phase proteins rises,lean tissue is catabolized to provide energy substrates for wound and inflammatory tissue.Plasma proteins drop due to inhibition of hepathic synthesis,an increase in capillary permeability,and the dilutional effect of extracellular fluid expansion can be observed.Muscle protein synthesis seems to be decreased.These changes are driven by a combination of the counterregulatory hormones (catecholamines,glucagon,cortisol,growth hormone) and the direct and indirect actions fo the various inflammatory mediators (IL-1,IL-6,and TNF),prostaglandins and kallikreins.The changes in whole body protein turnover seen in MOF are similar to those described in overt sepsis and severe trauma:both synthesis and degradation are elevated,with a higher rate of degradation.This situation result in a loss of body mass, predominantly lean tissue.Although it is not oftern possible to identify the orgin of the “sepsis”,it must be reasonable to regard patients with MOF metabolically as “severely septic”.In recent years,the gastrointestinal tract was

  18. MIL系列MOFs材料的合成及应用研究进展%Synthesis and Application of MIL-A Typical Series of MOFs

    Institute of Scientific and Technical Information of China (English)

    吴事剑; 王荷英; 李晗; 张镇坚

    2012-01-01

    金属有机骨架(Metal.OrganicFrameworks,MOFs)材料是一种新型功能材料。MIL系列材料作为MOFs材料的典型代表之一,有着广泛的应用前景。文章讨论了MIL系列材料的合成方法,总结了MIL系列材料在气体的储存和分离、多相催化、药物的存储和缓释以及光电磁等方面的应用,并对MIL系列新型多功能材料研究的发展趋势进行了展望。%Metal-Organic Frameworks(MOFs) are a new class of functional materials. Materials of Institute Lavoisier Frameworks(MIL) are a typical series of MOFs that have been proved to be very promising in many fields, such as gas adsorption and separation, catalysis, magnetism and drag storage and controlled-release In the review, the common synthesis methods of MIL materials were introduced, and the progresses of the materials on gas adsorption and separation, catalysis, magnetism as well as drug storage and controlled-release in recent years were also summarized here. At last, the development trends of MIL as functional materials were discussed.

  19. Photonic Crystal Sensors Based on Porous Silicon

    Directory of Open Access Journals (Sweden)

    Claudia Pacholski

    2013-04-01

    Full Text Available Porous silicon has been established as an excellent sensing platform for the optical detection of hazardous chemicals and biomolecular interactions such as DNA hybridization, antigen/antibody binding, and enzymatic reactions. Its porous nature provides a high surface area within a small volume, which can be easily controlled by changing the pore sizes. As the porosity and consequently the refractive index of an etched porous silicon layer depends on the electrochemial etching conditions photonic crystals composed of multilayered porous silicon films with well-resolved and narrow optical reflectivity features can easily be obtained. The prominent optical response of the photonic crystal decreases the detection limit and therefore increases the sensitivity of porous silicon sensors in comparison to sensors utilizing Fabry-Pérot based optical transduction. Development of porous silicon photonic crystal sensors which allow for the detection of analytes by the naked eye using a simple color change or the fabrication of stacked porous silicon photonic crystals showing two distinct optical features which can be utilized for the discrimination of analytes emphasize its high application potential.

  20. Hierarchical Sandwich-Like Structure of Ultrafine N-Rich Porous Carbon Nanospheres Grown on Graphene Sheets as Superior Lithium-Ion Battery Anodes.

    Science.gov (United States)

    Xie, Zhiqiang; He, Ziyang; Feng, Xuhui; Xu, Wangwang; Cui, Xiaodan; Zhang, Jiuhong; Yan, Cheng; Carreon, Moises A; Liu, Zheng; Wang, Ying

    2016-04-27

    A sandwich-like, graphene-based porous nitrogen-doped carbon (PNCs@Gr) has been prepared through facile pyrolysis of zeolitic imidazolate framework nanoparticles in situ grown on graphene oxide (GO) (ZIF-8@GO). Such sandwich-like nanostructure can be used as anode material in lithium ion batteries, exhibiting remarkable capacities, outstanding rate capability, and cycling performances that are some of the best results among carbonaceous electrode materials and exceed most metal oxide-based anode materials derived from metal orgainc frameworks (MOFs). Apart from a high initial capacity of 1378 mAh g(-1) at 100 mA g(-1), this PNCs@Gr electrode can be cycled at high specific currents of 500 and 1000 mA g(-1) with very stable reversible capacities of 1070 and 948 mAh g(-1) to 100 and 200 cycles, respectively. At a higher specific current of 5000 mA g(-1), the electrode still delivers a reversible capacity of over 530 mAh g(-1) after 400 cycles, showing a capacity retention of as high as 84.4%. Such an impressive electrochemical performance is ascribed to the ideal combination of hierarchically porous structure, a highly conductive graphene platform, and high-level nitrogen doping in the sandwich-like PNCs@Gr electrode obtained via in situ synthesis.

  1. Additive manufacturing technologies of porous metal implants

    Institute of Scientific and Technical Information of China (English)

    Zhou Linxi; Yang Quanzhan; Zhang Guirong; Zhao Fangxin; Shen Gang; Yu Bo

    2014-01-01

    Biomedical metal materials with good corrosion resistance and mechanical properties are widely used in orthopedic surgery and dental implant materials, but they can easily cause stress shielding due to the signiifcant difference in elastic modulus between the implant and human bones. The elastic modulus of porous metals is lower than that of dense metals. Therefore, it is possible to adjust the pore parameters to make the elastic modulus of porous metals match or be comparable with that of the bone tissue. At the same time, the open porous metals with pores connected to each other could provide the structural condition for bone ingrowth, which is helpful in strengthening the biological combination of bone tissue with the implants. Therefore, the preparation technologies of porous metal implants and related research have been drawing more and more attention due to the excellent features of porous metals. Selective laser melting (SLM) and electron beam melting technology (EBM) are important research fields of additive manufacturing. They have the advantages of directly forming arbitrarily complex shaped metal parts which are suitable for the preparation of porous metal implants with complex shape and ifne structure. As new manufacturing technologies, the applications of SLM and EBM for porous metal implants have just begun. This paper aims to understand the technology status of SLM and EBM, the research progress of porous metal implants preparation by using SLM and EBM, and the biological compatibility of the materials, individual design and manufacturing requirements. The existing problems and future research directions for porous metal implants prepared by SLM and EBM methods are discussed in the last paragraph.

  2. Additive manufacturing technologies of porous metal implants

    Directory of Open Access Journals (Sweden)

    Yang Quanzhan

    2014-06-01

    Full Text Available Biomedical metal materials with good corrosion resistance and mechanical properties are widely used in orthopedic surgery and dental implant materials, but they can easily cause stress shielding due to the significant difference in elastic modulus between the implant and human bones. The elastic modulus of porous metals is lower than that of dense metals. Therefore, it is possible to adjust the pore parameters to make the elastic modulus of porous metals match or be comparable with that of the bone tissue. At the same time, the open porous metals with pores connected to each other could provide the structural condition for bone ingrowth, which is helpful in strengthening the biological combination of bone tissue with the implants. Therefore, the preparation technologies of porous metal implants and related research have been drawing more and more attention due to the excellent features of porous metals. Selective laser melting (SLM and electron beam melting technology (EBM are important research fields of additive manufacturing. They have the advantages of directly forming arbitrarily complex shaped metal parts which are suitable for the preparation of porous metal implants with complex shape and fine structure. As new manufacturing technologies, the applications of SLM and EBM for porous metal implants have just begun. This paper aims to understand the technology status of SLM and EBM, the research progress of porous metal implants preparation by using SLM and EBM, and the biological compatibility of the materials, individual design and manufacturing requirements. The existing problems and future research directions for porous metal implants prepared by SLM and EBM methods are discussed in the last paragraph.

  3. Hydrodynamic dispersion within porous biofilms

    KAUST Repository

    Davit, Y.

    2013-01-23

    Many microorganisms live within surface-associated consortia, termed biofilms, that can form intricate porous structures interspersed with a network of fluid channels. In such systems, transport phenomena, including flow and advection, regulate various aspects of cell behavior by controlling nutrient supply, evacuation of waste products, and permeation of antimicrobial agents. This study presents multiscale analysis of solute transport in these porous biofilms. We start our analysis with a channel-scale description of mass transport and use the method of volume averaging to derive a set of homogenized equations at the biofilm-scale in the case where the width of the channels is significantly smaller than the thickness of the biofilm. We show that solute transport may be described via two coupled partial differential equations or telegrapher\\'s equations for the averaged concentrations. These models are particularly relevant for chemicals, such as some antimicrobial agents, that penetrate cell clusters very slowly. In most cases, especially for nutrients, solute penetration is faster, and transport can be described via an advection-dispersion equation. In this simpler case, the effective diffusion is characterized by a second-order tensor whose components depend on (1) the topology of the channels\\' network; (2) the solute\\'s diffusion coefficients in the fluid and the cell clusters; (3) hydrodynamic dispersion effects; and (4) an additional dispersion term intrinsic to the two-phase configuration. Although solute transport in biofilms is commonly thought to be diffusion dominated, this analysis shows that hydrodynamic dispersion effects may significantly contribute to transport. © 2013 American Physical Society.

  4. Fabrication of integrated porous glass for microfluidic applications

    NARCIS (Netherlands)

    Sukas, S.; Tiggelaar, R.M.; Desmet, G.; Gardeniers, J.G.E.

    2013-01-01

    This paper presents a method for the fabrication of integrated porous silica layers in microfluidic channel networks by microfabrication techniques. Porous silica is obtained by anodization of silicon, followed by full conversion of the porous silicon network into porous silica by means of thermal o

  5. Porous Iron Structure Fabrication and Characterization

    OpenAIRE

    Kim, Taewoo

    2015-01-01

    Porous iron or steel structures can be useful as light- weight materials for transportation and structural applications. We have created such porous iron metallic structures by utilizing a composite of Fe2O3 nanoparticles(NPs), poly(methyl methacrylate)(PMMA) beads and polyethylene glycol(PEG) binder resin. Final optimized porous iron structure contains micro-pores of 15-20 µm size and nano-pores of 100-500 nm with strong connections between Fe grains. The results indicate that further effort...

  6. A new stereolithography experimental porous flow device

    Energy Technology Data Exchange (ETDEWEB)

    Crandall, D.M.; Ahmadi, G. (Clarkson Univ., Potsdam, NY); Leonard, D. (Clarkson Univ., Potsdam, NY); Ferer, M.V.; Smith, D.H.

    2008-04-11

    A new method for constructing laboratory-scale porous media with increased pore-level variabilities for two-phase flow experiments is presented here. These devices have been created with stereolithography directly on glass, thus improving the stability of the model created with this precision rapid construction technique. The method of construction and improved parameters are discussed in detail, followed by a brief comparison of two-phase drainage results for air invasion into the water-saturated porous medium. Flow through the model porous medium is shown to substantiate theoretical fractal predictions.

  7. Porous and Nanoporous Semiconductors and Emerging Applications

    Directory of Open Access Journals (Sweden)

    Helmut Föll

    2006-01-01

    Full Text Available Pores in single-crystalline semiconductors can be produced in a wide range of geometries and morphologies, including the “nanometer” regime. Porous semiconductors may have properties completely different from the bulk, and metamaterials with, for example, optical properties not encountered in natural materials are emerging. Possible applications of porous semiconductors include various novel sensors, but also more “exotic” uses as, for example, high explosives or electrodes for micro-fuel cells. The paper briefly reviews pore formation (including more applied aspects of large area etching, properties of porous semiconductors, and emerging applications.

  8. Tritium transport in lithium ceramics porous media

    Energy Technology Data Exchange (ETDEWEB)

    Tam, S.W.; Ambrose, V.

    1991-12-31

    A random network model has been utilized to analyze the problem of tritium percolation through porous Li ceramic breeders. Local transport in each pore channel is described by a set of convection-diffusion-reaction equations. Long range transport is described by a matrix technique. The heterogeneous structure of the porous medium is accounted for via Monte Carlo methods. The model was then applied to an analysis of the relative contribution of diffusion and convective flow to tritium transport in porous lithium ceramics. 15 refs., 4 figs.

  9. Tritium transport in lithium ceramics porous media

    Energy Technology Data Exchange (ETDEWEB)

    Tam, S.W.; Ambrose, V.

    1991-01-01

    A random network model has been utilized to analyze the problem of tritium percolation through porous Li ceramic breeders. Local transport in each pore channel is described by a set of convection-diffusion-reaction equations. Long range transport is described by a matrix technique. The heterogeneous structure of the porous medium is accounted for via Monte Carlo methods. The model was then applied to an analysis of the relative contribution of diffusion and convective flow to tritium transport in porous lithium ceramics. 15 refs., 4 figs.

  10. A new stereolithography experimental porous flow device.

    Science.gov (United States)

    Crandall, Dustin; Ahmadi, Goodarz; Leonard, Douglas; Ferer, Martin; Smith, Duane H

    2008-04-01

    A new method for constructing laboratory-scale porous media with increased pore-level variabilities for two-phase flow experiments is presented here. These devices have been created with stereolithography directly on glass, thus improving the stability of the model created with this precision rapid construction technique. The method of construction and improved parameters are discussed in detail, followed by a brief comparison of two-phase drainage results for air invasion into the water-saturated porous medium. Flow through the model porous medium is shown to substantiate theoretical fractal predictions.

  11. Introduction of π-Complexation into Porous Aromatic Framework for Highly Selective Adsorption of Ethylene over Ethane

    Energy Technology Data Exchange (ETDEWEB)

    Li, Baiyan; Zhang, Yiming; Krishna, Rajamani; Yao, Kexin; Han, Yu; Wu, Zili; Ma, Dingxuan; Shi, Zhan; Pham, Tony; Space, Brian; Liu, Jian; Thallapally, Praveen K.; Liu, Jun; Matthew, Chrzanowski; Ma, Shengqian

    2014-06-05

    We report herein a strategy of incorporating air stable Ag(I) ions into water stable, high surface area porous organic polymer (POP) affording significant increase in ethylene uptake capacity and extremely high Qst for ethylene (over 100 kJ/mol at low ethylene load-ing) as illustrated in the context of Ag(I) ion functionalized PAF-1, PAF-1-SO3Ag. IAST calculations using single-component-isotherm data and equimolar ethylene/ethane ratio at 296 K reveal PAF-1-SO3Ag shows exceptionally high ethylene/ethane adsorption selectivi-ty (Sads: 27 to 125), far surpassing benchmark zeolite and any other MOF reported in literature. This alongside excellent water/air stability, high ethylene uptake capacity, and mild regeneration requirements make PAF-1-SO3Ag hold promise for adsorption-based eth-ylene/ethane separations, paving a way to develop Ag(I) ion function-alized POPs as a new platform for highly selective adsorption of eth-ylene over ethane.

  12. Synthesis of hierarchical porous carbon monoliths with incorporated metal-organic frameworks for enhancing volumetric based CO₂ capture capability.

    Science.gov (United States)

    Qian, Dan; Lei, Cheng; Hao, Guang-Ping; Li, Wen-Cui; Lu, An-Hui

    2012-11-01

    This work aims to optimize the structural features of hierarchical porous carbon monolith (HCM) by incorporating the advantages of metal-organic frameworks (MOFs) (Cu₃(BTC)₂) to maximize the volumetric based CO₂ capture capability (CO₂ capacity in cm³ per cm³ adsorbent), which is seriously required for the practical application of CO₂ capture. The monolithic HCM was used as a matrix, in which Cu₃(BTC)₂ was in situ synthesized, to form HCM-Cu₃(BTC)₂ composites by a step-by-step impregnation and crystallization method. The resulted HCM-Cu₃(BTC)₂ composites, which retain the monolithic shape and exhibit unique hybrid structure features of both HCM and Cu₃(BTC)₂, show high CO₂ uptake of 22.7 cm³ cm⁻³ on a volumetric basis. This value is nearly as twice as the uptake of original HCM. The dynamic gas separation measurement of HCM-Cu₃(BTC)₂, using 16% (v/v) CO₂ in N₂ as feedstock, illustrates that CO₂ can be easily separated from N₂ under the ambient conditions and achieves a high separation factor for CO₂ over N₂, ranging from 67 to 100, reflecting a strongly competitive CO₂ adsorption by the composite. A facile CO₂ release can be realized by purging an argon flow through the fixed-bed adsorber at 25 °C, indicating the good regeneration ability.

  13. Techniques for the Preparation of Porous Metals

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Porous metals have been developed greatly and swiftly in recent years. In this paper, main types of these materials are described briefly, and their preparation methods are related primarily, with the purpose offering some clues for optimizing the producing technology.

  14. Thermal effects in orthotropic porous elastic beams

    Science.gov (United States)

    Iaşan, D.

    2009-01-01

    This paper is concerned with the linear theory of anisotropic porous elastic bodies. The extension and bending of orthotropic porous elastic cylinders subjected to a plane temperature field is investigated. The work is motivated by the recent interest in the using of the orthotropic porous elastic solid as model for bones and various engineering materials. First, the thermoelastic deformation of inhomogeneous beams whose constitutive coefficients are independent of the axial coordinate is studied. Then, the extension and bending effects in orthotropic cylinders reinforced by longitudinal rods are investigated. The three-dimensional problem is reduced to the study of two-dimensional problems. The method is used to solve the problem of an orthotropic porous circular cylinder with a special kind of inhomogeneity.

  15. Multiphase flow in fractured porous media

    Energy Technology Data Exchange (ETDEWEB)

    Firoozabadi, A.

    1995-02-01

    The major goal of this research project was to improve the understanding of the gas-oil two-phase flow in fractured porous media. In addition, miscible displacement was studied to evaluate its promise for enhanced recovery.

  16. Adsorption on Highly Ordered Porous Alumina

    Science.gov (United States)

    Mistura, Giampaolo; Bruschi, Lorenzo; Lee, Woo

    2016-10-01

    Porous anodic aluminum oxide (AAO) is characterized by a regular arrangement of the pores with a narrow pore size distribution over extended areas, uniform pore depth, and solid pore walls without micropores. Thanks to significant improvements in anodization techniques, structural engineering of AAO allows to accurately tailor the pore morphology. These features make porous AAO an excellent substrate to study adsorption phenomena. In this paper, we review recent experiments involving the adsorption in porous AAO. Particular attention will be devoted to adsorption in straight and structured pores with a closed end which shed new light on fundamental issues like the origin of hysteresis in closed end pores and the nature of evaporation from ink-bottle pores. The results will be compared to those obtained in other synthetic materials like porous silicon and silica.

  17. Photodetectors on the Basis of Porous Silicon

    Directory of Open Access Journals (Sweden)

    I.B. Olenych

    2012-11-01

    Full Text Available The paper studies the electrical characteristics of photodiode structures porous silicon – silicon substrates modified with molecules of iodine. Changes the nature of current-voltage characteristics obtained structures with symmetrical for straightening result of adsorption of iodine are revealed. It is studied the spectral characteristics of photoresponse in the 450-1100 nm wavelength range, its temperature dependence in the 125-325 K range and energy characteristics of photovoltaic structures based on porous silicon. A possible mechanism of influence of iodine adsorption on the electrical and photoelectrical properties of the structures of porous silicon – silicon substrates is proposed. The results extend the perspectives of porous silicon in photoelectronics.

  18. Fabrication of porous hydroxyapatite by foam technique

    Energy Technology Data Exchange (ETDEWEB)

    Abdullah, Y.; Reusmaazran Yusof, M.; Besar, I.; Mustafa, R. [Malaysian Inst. for Nuclear Technology Research (MINT), Kajang, Selangor (Malaysia); Hing, K.A. [IRC in Biomedical Materials, Queen Mary and Westfield Coll., Univ. of London (United Kingdom)

    2002-07-01

    To improve healthcare, there is an increasing demand for bone replacement or bone graft materials towards treating and improving available parts of human body. Beside bioactive and biocompatible, synthetic hydroxyapatite can be produced with a porous structure to meet the requirement as a bone graft materials. In this work, the foam burnout technique was successfully used to produce porous hydroxyapatite. A polyurethane foam was soaked in a slip prepared by mixing hydroxyapatite powder with a binder solution prepared from polyvinylpyrolidone (PVP). After dried, the green structure was burnout and sintered. In this method, the prepared slip can influence the porous structure, hence gives rise to higher porosity and pore connectivity due to lower molecular weight binder (PVP). This paper presents the physical and morphological characteristics of the porous structure produced. (orig.)

  19. Methane storage in advanced porous materials.

    Science.gov (United States)

    Makal, Trevor A; Li, Jian-Rong; Lu, Weigang; Zhou, Hong-Cai

    2012-12-01

    The need for alternative fuels is greater now than ever before. With considerable sources available and low pollution factor, methane is a natural choice as petroleum replacement in cars and other mobile applications. However, efficient storage methods are still lacking to implement the application of methane in the automotive industry. Advanced porous materials, metal-organic frameworks and porous organic polymers, have received considerable attention in sorptive storage applications owing to their exceptionally high surface areas and chemically-tunable structures. In this critical review we provide an overview of the current status of the application of these two types of advanced porous materials in the storage of methane. Examples of materials exhibiting high methane storage capacities are analyzed and methods for increasing the applicability of these advanced porous materials in methane storage technologies described. PMID:22990753

  20. Phase Transformation Dynamics in Porous Battery Electrodes

    CERN Document Server

    Ferguson, Todd R

    2014-01-01

    Porous electrodes composed of multiphase active materials are widely used in Li-ion batteries, but their dynamics are poorly understood. Two-phase models are largely empirical, and no models exist for three or more phases. Using a modified porous electrode theory based on non-equilibrium thermodynamics, we show that experimental phase behavior can be accurately predicted from free energy models, without artificially placing phase boundaries or fitting the open circuit voltage. First, we simulate lithium intercalation in porous iron phosphate, a popular two-phase cathode, and show that the zero-current voltage gap, sloping voltage plateau and under-estimated exchange currents all result from size-dependent nucleation and mosaic instability. Next, we simulate porous graphite, the standard anode with three stable phases, and reproduce experimentally observed fronts of color-changing phase transformations. These results provide a framework for physics-based design and control for electrochemical systems with comp...

  1. Adsorption on Highly Ordered Porous Alumina

    Science.gov (United States)

    Mistura, Giampaolo; Bruschi, Lorenzo; Lee, Woo

    2016-04-01

    Porous anodic aluminum oxide (AAO) is characterized by a regular arrangement of the pores with a narrow pore size distribution over extended areas, uniform pore depth, and solid pore walls without micropores. Thanks to significant improvements in anodization techniques, structural engineering of AAO allows to accurately tailor the pore morphology. These features make porous AAO an excellent substrate to study adsorption phenomena. In this paper, we review recent experiments involving the adsorption in porous AAO. Particular attention will be devoted to adsorption in straight and structured pores with a closed end which shed new light on fundamental issues like the origin of hysteresis in closed end pores and the nature of evaporation from ink-bottle pores. The results will be compared to those obtained in other synthetic materials like porous silicon and silica.

  2. Synthesis and electrochemical capacitive properties of nitrogen-doped porous carbon micropolyhedra by direct carbonization of zeolitic imidazolate framework-11

    Energy Technology Data Exchange (ETDEWEB)

    Hao, Fei; Li, Li; Zhang, Xiaohua, E-mail: mickyxie@hnu.edu.cn; Chen, Jinhua, E-mail: chenjinhua@hnu.edu.cn

    2015-06-15

    Highlights: • Nitrogen-doped porous carbon micropolyhedra (N-PCMPs) were prepared from ZIF-11. • The activated N-PCMPs with fused KOH (N-PCMPs-A) have high specific surface area. • N-PCMPs-A exhibits high specific capacitance. • N-PCMPs-A reveals good cycling performance even at a high current density. - Abstract: Nitrogen-doped porous carbon micropolyhedra (N-PCMPs) were successfully prepared by direct carbonization of ZIF-11 polyhedra and further activated with fused KOH to obtain N-PCMPs-A. The morphology and microstructure of samples were examined by scanning electron microscopy, X-ray diffraction, and micropore and chemisorption analyzer. Electrochemical properties were characterized by cyclic voltammetry and galvanostatic charge/discharge method in 1.0 M H{sub 2}SO{sub 4} aqueous solution on a standard three-electrode system. Results show that, compared with N-PCMPs, N-PCMPs-A has higher specific surface area (2188 m{sup 2} g{sup −1}) and exhibits improved electrochemical capacitive properties (307 F g{sup −1} at 1.0 A g{sup −1}). The mass specific capacitance of N-PCMPs-A is also higher than that of most MOF-derived carbons, some carbide-derived carbons and carbon aerogel-derived carbons. In addition, the capacitance of the N-PCMPs-A retains 90% after 4000 cycles even at a high current density of 10 A g{sup −1}. These imply that N-PCMPs-A is the promising materials for the construction of a high-performance supercapacitor.

  3. Synthesis and electrochemical capacitive properties of nitrogen-doped porous carbon micropolyhedra by direct carbonization of zeolitic imidazolate framework-11

    International Nuclear Information System (INIS)

    Highlights: • Nitrogen-doped porous carbon micropolyhedra (N-PCMPs) were prepared from ZIF-11. • The activated N-PCMPs with fused KOH (N-PCMPs-A) have high specific surface area. • N-PCMPs-A exhibits high specific capacitance. • N-PCMPs-A reveals good cycling performance even at a high current density. - Abstract: Nitrogen-doped porous carbon micropolyhedra (N-PCMPs) were successfully prepared by direct carbonization of ZIF-11 polyhedra and further activated with fused KOH to obtain N-PCMPs-A. The morphology and microstructure of samples were examined by scanning electron microscopy, X-ray diffraction, and micropore and chemisorption analyzer. Electrochemical properties were characterized by cyclic voltammetry and galvanostatic charge/discharge method in 1.0 M H2SO4 aqueous solution on a standard three-electrode system. Results show that, compared with N-PCMPs, N-PCMPs-A has higher specific surface area (2188 m2 g−1) and exhibits improved electrochemical capacitive properties (307 F g−1 at 1.0 A g−1). The mass specific capacitance of N-PCMPs-A is also higher than that of most MOF-derived carbons, some carbide-derived carbons and carbon aerogel-derived carbons. In addition, the capacitance of the N-PCMPs-A retains 90% after 4000 cycles even at a high current density of 10 A g−1. These imply that N-PCMPs-A is the promising materials for the construction of a high-performance supercapacitor

  4. Additive manufacturing technologies of porous metal implants

    OpenAIRE

    Yang Quanzhan; Zhang Guirong

    2014-01-01

    Biomedical metal materials with good corrosion resistance and mechanical properties are widely used in orthopedic surgery and dental implant materials, but they can easily cause stress shielding due to the significant difference in elastic modulus between the implant and human bones. The elastic modulus of porous metals is lower than that of dense metals. Therefore, it is possible to adjust the pore parameters to make the elastic modulus of porous metals match or be comparable with that of th...

  5. Multiparticle collision dynamics in porous media

    CERN Document Server

    Matyka, Maciej

    2016-01-01

    We adopt the multiparticle collision dynamics method to simulate fluid flows in porous media. For this, the particle-level drag force is introduced into the original algorithm. The force hinder the flow resulting in global resistance and decrease of permeability. The extended algorithm is validated in the flow through fully porous channel with analytical solution. Basic properties of the solver are investigated including its dependency of permeability on model parameters.

  6. Large deformations of a soft porous material

    OpenAIRE

    MacMinn, Christopher W.; Dufresne, Eric R.; Wettlaufer, John S.

    2015-01-01

    Compressing a porous material will decrease the volume of the pore space, driving fluid out. Similarly, injecting fluid into a porous material can expand the pore space, distorting the solid skeleton. This poromechanical coupling has applications ranging from tissue mechanics to hydrogeology. The classical theory of linear poroelasticity captures this coupling by combining Darcy's law with Terzaghi's effective stress and linear elasticity in a linearized kinematic framework. Linear poroelasti...

  7. Porous-core honeycomb bandgap THz fiber

    DEFF Research Database (Denmark)

    Nielsen, Kristian; Rasmussen, Henrik K.; Jepsen, Peter Uhd;

    2011-01-01

    In this Letter we propose a novel (to our knowledge) porous-core honeycomb bandgap design. The holes of the porous core are the same size as the holes in the surrounding cladding, thereby giving the proposed fiber important manufacturing benefits. The fiber is shown to have a 0:35-THz......-wide fundamental bandgap centered at 1:05 THz. The calculated minimum loss of the fiber is 0:25 dB=cm....

  8. Radionuclide trap studies using porous carbon

    International Nuclear Information System (INIS)

    Towards import substitute, an attempt has been made to synthesise porous carbon by acidic sucrose solution route for use as trap material for cesium isotopes. The radionuclide trap experiments have been carried out to study the uptake of fission product cesium (137Cs) using reticulated vitreous carbon (RVC) and home made porous carbon (HMPC) in static sodium system. The trapping efficiency and distribution coefficient have been measured and compared. (author)

  9. Porous Cellulose Materials from Nano Fibrillated Cellulose

    OpenAIRE

    Cervin, Nicholas

    2012-01-01

    In the first part of this work a novel type of low-density, sponge-like material for the separation of mixtures of oil and water has been prepared by vapour deposition of hydrophobic silanes on ultra-porous nanocellulose aerogels. To achieve this, a highly porous (> 99 %) nanocellulose aerogel with high structural flexibility and robustness is first formed by freeze-drying an aqueous dispersion of the nanocellulose. The density, pore size distribution and wetting properties of the aerogel ...

  10. MoF6在NaF颗粒上的吸附平衡及吸附动力学%Adsorption equilibrium and kinetics of molybdenum hexafluoride on sodium fluoride adsorbent

    Institute of Scientific and Technical Information of China (English)

    程治强; 李杨娟; 张国欣; 张焕琦; 李洒洒; 窦强; 龙德武; 吴国忠; 李晴暖

    2015-01-01

    为阐明六氟化钼(Molybdenum hexafluoride, MoF6)在氟化钠(Sodium fluoride, NaF)颗粒上的吸附机制,在静态吸附实验装置上研究了MoF6在NaF颗粒上的吸附平衡及吸附动力学行为,结果表明在50−100ºC内,NaF颗粒对MoF6的吸附速率和平衡吸附量随着温度而升高,在100ºC平衡吸附量达到115mg MoF6·g−1 NaF。当温度超过100ºC时,NaF对MoF6的吸附作用减弱,吸附量减小。Langmuir模型能较好描述NaF颗粒对MoF6的吸附过程,并推测MoF6在NaF颗粒上的吸附为单分子层吸附。吸附动力学模型分析表明,NaF颗粒对MoF6的吸附符合准二级动力学方程,同时吸附过程受到颗粒内扩散控制,但其并不是唯一速率控制步骤。%Background:The fluoride volatility processhas been developed to recover uranium from spent nuclear fuel. And the fluoride adsorption and desorption technique is usually applied to the purification of UF6 in the fluoride volatility process.Purpose: This study aims to investigate the adsorption mechanism of MoF6 on NaF adsorbent. Methods: The adsorption equilibrium and kinetics of MoF6 on NaF adsorbent at different temperatures and initial MoF6 pressure were experimentally studied by using statistic adsorption equipment. Langmuir adsorption model and adsorption kinetics model were applied to analyse experimental data.Results:The adsorption rate and equilibrium adsorption capacity of MoF6 on NaF adsorbent increased with the temperature increasing from 50 ºC to 100 ºC, and the adsorption capacity was 115 mg MoF6·g−1 NaF at 100 ºC.The experimental data were fitted by pseudo-second-order kinetics as well as Langmuir adsorption model.Conclusion:The adsorption of MoF6on NaF adsorbent was monolayer adsorption according to Langmuir adsorption model, and was controlled by diffusion of MoF6 inside NaF adsorbent which was not the unique rate-determining step, though.

  11. Template-Free Synthesis of Hierarchical Porous Metal-Organic Frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Yue, Yanfeng [ORNL; Qiao, Zhen-an [University of Tennessee, Knoxville (UTK); Fulvio, Pasquale F [ORNL; Dai, Sheng [ORNL; Binder, Andrew J [ORNL; Tian, Chengcheng [ORNL; Nelson, Kimberly M [ORNL; Zhu, Xiang [ORNL

    2013-01-01

    A template-free synthesis of a hierarchical microporous-mesoporous metal-organic framework (MOF) of Zn(II)-2,5-dihydroxy-1,4-benzenedicarboxylate, namely Zn-MOF-74, is reported. The surface morphology and porosity of the bimodal materials can be modified by etching the pore walls with the synthesis solvent under different reaction times and different solvents. This template-free strategy allows for the preparation of stable frameworks with mesopores exceeding 15 nm, which was previously unattained by the synthesis of MOFs by ligand exten-sion method.

  12. Exceptional gravimetric and volumetric CO2 uptake in a palladated NbO-type MOF utilizing cooperative acidic and basic, metal-CO2 interactions.

    Science.gov (United States)

    Spanopoulos, I; Bratsos, I; Tampaxis, C; Vourloumis, D; Klontzas, E; Froudakis, G E; Charalambopoulou, G; Steriotis, T A; Trikalitis, P N

    2016-08-18

    A novel NbO-type MOF is reported based on a palladated organic linker, showing a remarkable gravimetric and volumetric CO2 uptake, reaching 201.8 cm(3) g(-1) (9.0 mmol g(-1), 39.7 wt%) and 187.8 cm(3) cm(-3) at 273 K and 1 bar, respectively. Accurate theoretical calculations revealed that the exceptional CO2 uptake is due to the combination of Lewis base Pd(ii)-CO2 (24.3 kJ mol(-1)) and Lewis acid Cu(ii)-CO2 (30.3 kJ mol(-1)) interactions, as well as synergistic pore size effects. PMID:27498783

  13. A novel 3D Ag(I)-MOF: Surfactant-directed syntheses and catalytic degradation of o/m/p-Nitrophenol

    Science.gov (United States)

    Wu, Xue-Qian; Wen, Guo-Xuan; Wu, Ya-Pan; Dong, Wen-Wen; Zhao, Jun; Li, Dong-Sheng

    2016-10-01

    For the first time, sodium caprylate has been investigated to direct the crystal growth of 3D Ag-MOF, [Ag2(ddcba)(4,4‧-bipy)2] (1), constructing from 3,5-(di(2‧,5‧-dicarboxylphenyl)benozoic acid and 4,4‧-bipy. The single crystal diffraction analyses shows that complex 1 possess 3D neutral framework with a three-connected ThSi2 (103-b) topology. Compound 1 exhibits predominant catalytic activity towards the degradation of o-Nitrophenol (ONP), m-Nitrophenol (MNP) and p-Nitrophenol (PNP) in aqueous solution. The kinetics of such catalytic degradation reactions was also studied.

  14. Pore Structure Reconstruction and Moisture Migration in Porous Media

    Science.gov (United States)

    Zheng, Jiayi; Shi, Xing; Shi, Juan; Chen, Zhenqian

    2014-09-01

    Three kinds of porous media (isotropic, perpendicular anisotropic and parallel anisotropic porous media) with the same porosity, different pore size distributions and fractal spectral dimensions were reconstructed by random growth method. It was aimed to theoretically study the impact of microscopic pore structure on water vapor diffusion process in porous media. The results show that pore size distribution can only denote the static characteristics of porous media but cannot effectively reflect the dynamic transport characteristics of porous media. Fractal spectral dimension can effectively analyze and reflect pores connectivity and moisture dynamic transport properties of porous media from the microscopic perspective. The pores connectivity and water vapor diffusion performance in pores of porous media get better with the increase of fractal spectral dimension of porous media. Fractal spectral dimension of parallel anisotropic porous media is more than that of perpendicular anisotropic porous media. Fractal spectral dimension of isotropic porous media is between parallel anisotropic porous media and perpendicular anisotropic porous media. Other macroscopic parameters such as equilibrium diffusion coefficient of water vapor, water vapor concentration variation at right boundary in equilibrium, the time when water vapor diffusion process reaches a stable state also can characterize the pores connectivity and water vapor diffusion properties of porous media.

  15. Peristaltic transport of a Maxwell fluid in a porous asymmetric channel through a porous medium

    Directory of Open Access Journals (Sweden)

    Safia Akram

    2014-12-01

    Full Text Available The present study investigates the peristaltic flow of a Maxwell fluid in a porous asymmetric channel through a porous medium. An analytical solution has been found using regular perturbation method. The stream function and average mean velocity are obtained. The graphical results are presented to discuss the physical behavior of various parameters appearing in the problem.

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

    Science.gov (United States)

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

    2016-07-01

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

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

    Science.gov (United States)

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

    2016-07-01

    Activated carbon (AC) composite with HKUST-1 metal organic framework (AC-HKUST-1 MOF) was prepared by ultrasonically assisted hydrothermal method and characterized by FTIR, SEM and XRD analysis and laterally was applied for the simultaneous ultrasound-assisted removal of crystal violet (CV), disulfine blue (DSB) and quinoline yellow (QY) dyes in their ternary solution. In addition, this material, was screened in vitro for their antibacterial actively against Methicillin-resistant Staphylococcus aureus (MRSA) and Pseudomonas aeruginosa (PAO1) bacteria. In dyes removal process, the effects of important variables such as initial concentration of dyes, adsorbent mass, pH and sonication time on adsorption process optimized by Taguchi approach. Optimum values of 4, 0.02g, 4min, 10mgL(-1) were obtained for pH, AC-HKUST-1 MOF mass, sonication time and the concentration of each dye, respectively. At the optimized condition, the removal percentages of CV, DSB and QY were found to be 99.76%, 91.10%, and 90.75%, respectively, with desirability of 0.989. Kinetics of adsorption processes follow pseudo-second-order model. The Langmuir model as best method with high applicability for representation of experimental data, while maximum mono layer adsorption capacity for CV, DSB and QY on AC-HKUST-1 estimated to be 133.33, 129.87 and 65.37mgg(-1) which significantly were higher than HKUST-1 as sole material with Qm to equate 59.45, 57.14 and 38.80mgg(-1), respectively. PMID:26964963

  18. From porous gold nanocups to porous nanospheres and solid particles - A new synthetic approach

    KAUST Repository

    Ihsan, Ayesha

    2015-05-01

    We report a versatile approach for the synthesis of porous gold nanocups, porous gold nanospheres and solid gold nanoparticles. Gold nanocups are formed by the slow reduction of gold salt (HAuCl4{dot operator}3H2O) using aminoantipyrene (AAP) as a reducing agent. Adding polyvinylpyrrolidone (PVP) to the gold salt followed by reduction with AAP resulted in the formation of porous gold nanospheres. Microwave irradiation of both of these porous gold particles resulted in the formation of slightly smaller but solid gold particles. All these nanoparticles are thoroughly characterized by UV-visible spectroscopy, scanning electron microscopy (SEM), high resolution transmission electron microscopy (HR-TEM) and bright-field tomography. Due to the larger size, porous nature, low density and higher surface area, these nanomaterials may have interesting applications in catalysis, drug delivery, phototherapy and sensing.

  19. Erbium doped stain etched porous silicon

    Energy Technology Data Exchange (ETDEWEB)

    Gonzalez-Diaz, B. [Departamento de Fisica Basica, Universidad de La Laguna, Avda. Astrofisico Francisco Sanchez, 38204 La Laguna, S/C de Tenerife (Spain); Diaz-Herrera, B. [Departamento de Energia Fotovoltaica, Instituto Tecnologico de Energias Renovables (ITER), Poligono Industrial de Granadilla, 38611 S/C Tenerife (Spain); Guerrero-Lemus, R. [Departamento de Fisica Basica, Universidad de La Laguna, Avda. Astrofisico Francisco Sanchez, 38204 La Laguna, S/C de Tenerife (Spain)], E-mail: rglemus@ull.es; Mendez-Ramos, J.; Rodriguez, V.D. [Departamento de Fisica Fundamental, Experimental Electronica y Sistemas, Universidad de La Laguna, Avda. Astrofisico Francisco Sanchez, 38204 La Laguna, S/C de Tenerife (Spain); Hernandez-Rodriguez, C. [Departamento de Fisica Basica, Universidad de La Laguna, Avda. Astrofisico Francisco Sanchez, 38204 La Laguna, S/C de Tenerife (Spain); Martinez-Duart, J.M. [Departamento de Fisica Aplicada, C-XII, Universidad Autonoma de Madrid, 28049 Cantoblanco, Madrid (Spain)

    2008-01-15

    In this work a simple erbium doping process applied to stain etched porous silicon layers (PSLs) is proposed. This doping process has been developed for application in porous silicon solar cells, where conventional erbium doping processes are not affordable because of the high processing cost and technical difficulties. The PSLs were formed by immersion in a HF/HNO{sub 3} solution to properly adjust the porosity and pore thickness to an optimal doping of the porous structure. After the formation of the porous structure, the PSLs were analyzed by means of nitrogen BET (Brunauer, Emmett and Teller) area measurements and scanning electron microscopy. Subsequently, the PSLs were immersed in a saturated erbium nitrate solution in order to cover the porous surface. Then, the samples were subjected to a thermal process to activate the Er{sup 3+} ions. Different temperatures and annealing times were used in this process. The photoluminescence of the PSLs was evaluated before and after the doping processes and the composition was analyzed by Fourier transform IR spectroscopy.

  20. Flow past a porous approximate spherical shell

    Science.gov (United States)

    Srinivasacharya, D.

    2007-07-01

    In this paper, the creeping flow of an incompressible viscous liquid past a porous approximate spherical shell is considered. The flow in the free fluid region outside the shell and in the cavity region of the shell is governed by the Navier Stokes equation. The flow within the porous annulus region of the shell is governed by Darcy’s Law. The boundary conditions used at the interface are continuity of the normal velocity, continuity of the pressure and Beavers and Joseph slip condition. An exact solution for the problem is obtained. An expression for the drag on the porous approximate spherical shell is obtained. The drag experienced by the shell is evaluated numerically for several values of the parameters governing the flow.

  1. Electrochemical properties of porous bismuth electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Romann, T., E-mail: tavo.romann@ut.e [Institute of Chemistry, University of Tartu, Ravila 14A, 50411 Tartu (Estonia); Lust, E. [Institute of Chemistry, University of Tartu, Ravila 14A, 50411 Tartu (Estonia)

    2010-08-01

    The properties of Bi surfaces with different roughnesses were characterized by electron microscopy, cyclic voltammetry, and impedance spectroscopy. Two different strategies were used for preparation of porous bismuth layers onto Bi microelectrode surface in aqueous 0.1 M LiClO{sub 4} solution. Firstly, treatment at potential E < -2 V (vs. Ag|AgCl in sat. KCl) has been applied, resulting in bismuth hydride formation and decomposition into Bi nanoparticles which deposit at the electrode surface. Secondly, porous Bi layer was prepared by anodic dissolution (E = 1 V) of bismuth electrode followed by fast electroreduction of formed Bi{sup 3+} ions at cathodic potentials E = -2 V. The nanostructured porous bismuth electrode, with surface roughness factor up to 220, has negligible frequency dispersion of capacitance and higher hydrogen evolution overvoltage than observed for smooth Bi electrodes.

  2. Characterizations of PSD Fractal of Porous Medium

    Institute of Scientific and Technical Information of China (English)

    黄国强; 徐世民; 李鑫钢

    2003-01-01

    A volume-based method for measuring particle-size distribution (PSD) fractal dimensions of porous mediums was developed by employing laser size-analyzing technology. Compared with conventional approaches of using hydrometer or screen to determine PSD, this method can avoid calculation errors and measure smaller size-scale porous medium. In this paper the experimental porous mediums were brown soil, kaolin and sand soil. A micro-order of magnitude (10-5 m) in particle-size interval could be shown in PSD results of brown soil and kaolin. The experiments indicated that brown soil had a nearly mono-fractal PSD character, while kaolin and sand soil showed multi-fractal PSD characters. By the adsorption isotherm experiments, the PSD fractal dimensions of the sand soil were also found to keep a linearly increasing relation with the linear adsorptive parameters of the soils in different intervals to adsorb benzene from aqueous solution.

  3. Gas foamed open porous biodegradable polymeric microspheres.

    Science.gov (United States)

    Kim, Taek Kyoung; Yoon, Jun Jin; Lee, Doo Sung; Park, Tae Gwan

    2006-01-01

    Highly open porous biodegradable polymeric microspheres were fabricated for use as injectable scaffold microcarriers for cell delivery. A modified water-in-oil-in-water (W1/O/W2) double emulsion solvent evaporation method was employed for producing the microspheres. The incorporation of an effervescent salt, ammonium bicarbonate, in the primary W1 droplets spontaneously produced carbon dioxide and ammonia gas bubbles during the solvent evaporation process, which not only stabilized the primary emulsion, but also created well inter-connected pores in the resultant microspheres. The porous microspheres fabricated under various gas foaming conditions were characterized. The surface pores became as large as 20 microm in diameter with increasing the concentration of ammonium bicarbonate, being sufficient enough for cell infiltration and seeding. These porous scaffold microspheres could be potentially utilized for cultivating cells in a suspension manner and for delivering the seeded cells to the tissue defect site in an injectable manner. PMID:16023197

  4. Fluid dynamics in porous media with Sailfish

    Science.gov (United States)

    Coelho, Rodrigo C. V.; Neumann, Rodrigo F.

    2016-09-01

    In this work we show the application of Sailfish to the study of fluid dynamics in porous media. Sailfish is an open-source software based on the lattice-Boltzmann method. This application of computational fluid dynamics is of particular interest to the oil and gas industry and the subject could be a starting point for an undergraduate or graduate student in physics or engineering. We built artificial samples of porous media with different porosities and used Sailfish to simulate the fluid flow through them in order to calculate their permeability and tortuosity. We also present a simple way to obtain the specific superficial area of porous media using Python libraries. To contextualise these concepts, we analyse the applicability of the Kozeny-Carman equation, which is a well-known permeability-porosity relation, to our artificial samples.

  5. Cryptosporidium Parvum Transport Through Natural Porous Media

    Science.gov (United States)

    Araujo, J. B.; Santamaria, J.; Blandford, W. P.; Gerba, C. P.; Brusseau, M. L.

    2005-12-01

    The objective of this study was to quantify the transport of Cryptosporidium parvum through saturated natural porous media. A series of miscible-displacement experiments were conducted, varying the properties of the porous media and electrolyte solution to help elucidate retention mechanisms. Significant removal (~99%) of oocysts was observed for transport in a sandy soil. Similar removals were also observed for experiments conducted with deionized water in place of the 0.01M NaCl electrolyte solution and experiments with a sub sample of the sandy soil that was treated with nitric acid. Effluent recoveries were greater for experiments conducted using coarser porous media. These results indicate straining contributed to the retention of Cryptosporidium parvum in our system.

  6. Synthesis of Emulsion-templated Porous Polycaprolactone

    Directory of Open Access Journals (Sweden)

    Xiao Chenchen

    2016-01-01

    Full Text Available Emulsion-templated porous materials have gained extensively in applications due to their low density and high porosity. However, by far most this type porous polymers are synthesized using conventional radical polymerization and most of the reactions are thermally initiated. Expanding the polymerization mechanisms available for emulsion-templated polymers synthesis is still highly desired. In this work, Diel-Alder (DA reaction was used to synthesize emulsion-templated macroporous polycaprolactone (PCL. These macroporous polymers were prepared by DA reaction of polycaprolactone pendant with multiple furan group (PCL-furan and 1,6-bis(maleimidehexane (BisM via a high internal 1phase emulsion as template. The porous materials have a typical structure of emulsion-templated 2materials.

  7. Integrating Porous Resins In Enzymatic Processes

    DEFF Research Database (Denmark)

    Al-Haque, Naweed

    of these enzymes to be harnessed. Porous resins as opposed to other auxiliary phases, for example organic solvents, are nonbioavailable, biocompatible and offer simpler operational handling (no foaming and emulsification). This strategy has been applied effectively to single substrate – single product systems...... of integrating porous resins for multi-component systems. In this manner, a generic platform has been established for biocatalytic reactions that require the integration of this strategy. The framework identifies the key information about the reaction and the process using a step-wise protocol with the required...... tools. It includes the use of kinetic modelling in characterizing the reaction kinetics, a heuristic approach for screening resins and a model based approach for evaluating the process. Greater knowledge about the enzymatic processes with integrated porous resins can therefore be gained and thus...

  8. Fluid dynamics in porous media with Sailfish

    Science.gov (United States)

    Coelho, Rodrigo C. V.; Neumann, Rodrigo F.

    2016-09-01

    In this work we show the application of Sailfish to the study of fluid dynamics in porous media. Sailfish is an open-source software based on the lattice-Boltzmann method. This application of computational fluid dynamics is of particular interest to the oil and gas industry and the subject could be a starting point for an undergraduate or graduate student in physics or engineering. We built artificial samples of porous media with different porosities and used Sailfish to simulate the fluid flow through them in order to calculate their permeability and tortuosity. We also present a simple way to obtain the specific superficial area of porous media using Python libraries. To contextualise these concepts, we analyse the applicability of the Kozeny–Carman equation, which is a well-known permeability–porosity relation, to our artificial samples.

  9. Trends in modeling of porous media combustion

    Energy Technology Data Exchange (ETDEWEB)

    Mujeebu, M. Abdul; Abdullah, M. Zulkifly [Porous Media Combustion Laboratory, School of Mechanical Engineering, Universiti Sains Malaysia, Engineering Campus, 14300 Nibong Tebal, Penang (Malaysia); Mohamad, A.A. [College of Engineering, Alfaisal University, Riyadh 11533, P.O. Box 50927 (Saudi Arabia); Bakar, M.Z. Abu [School of Chemical Engineering, Universiti Sains Malaysia, Engineering Campus, 14300 Nibong Tebal, Penang (Malaysia)

    2010-12-15

    Porous media combustion (PMC) has interesting advantages compared with free flame combustion due to higher burning rates, increased power dynamic range, extension of the lean flammability limits, and low emissions of pollutants. Extensive experimental and numerical works were carried out and are still underway, to explore the feasibility of this interesting technology for practical applications. For this purpose, numerical modeling plays a crucial role in the design and development of promising PMC systems. This article provides an exhaustive review of the fundamental aspects and emerging trends in numerical modeling of gas combustion in porous media. The modeling works published to date are reviewed, classified according to their objectives and presented with general conclusions. Numerical modeling of liquid fuel combustion in porous media is excluded. (author)

  10. A liquid bridge connecting moving porous surfaces

    Science.gov (United States)

    Gharib, Morteza; Gat, Amir; Navaz, Homayun

    2011-11-01

    We study the coupled problem of a liquid bridge connecting two porous surfaces where the gap between the surfaces is an externally controlled function of time. The relative motion between the surfaces affects the geometry and the pressure distribution of the liquid bridge, thus influencing the diffusion speed and penetration topology within the porous material. Utilizing the lubrication approximation and Darcy's phenomenological law we obtain a relation between the diffusion into the porous surface and the relative motion between the surfaces. A scheme to control the diffusion topology is presented and illustrated for the case of conical penetration topology with an arbitrary cone opening angle. Analytic expressions describing the penetration topology for the case of constant speed of the surfaces and the relative motion between the surfaces required to create a conical penetration topology are obtained and compared to experimental and numerical data. This project was supported by the Defense Threat Reduction Agency (DTRA), Award Number: 330233-A.

  11. Fluid dynamics in porous media with Sailfish

    CERN Document Server

    Coelho, Rodrigo C V

    2016-01-01

    In this work we show the application of Sailfish to the study of fluid dynamics in porous media. Sailfish is an open-source software based on the lattice-Boltzmann method. This application of computational fluid dynamics is of particular interest to the oil and gas industry and the subject could be a starting point for an undergraduate or graduate student in physics or engineering. We built artificial samples of porous media with different porosities and used Sailfish to simulate the fluid flow through in order to calculate permeability and tortuosity. We also present a simple way to obtain the specific superficial area of porous media using Python libraries. To contextualize these concepts, we test the Kozeny--Carman equation, discuss its validity and calculate the Kozeny's constant for our artificial samples.

  12. Sorption properties of porous melamine formaldehyde resins

    Science.gov (United States)

    Deryło-Marczewska, Anna; Goworek, Jacek; Kusak, Ryszard; Zgrajka, Wojciech

    2002-07-01

    Three types of melamine-formaldehyde porous sorbents were synthesized by using the fumed silica as an inorganic template. The changes in polymerization conditions lead to a differentiation of the porosity and surface area of these materials. This synthesis allowed preparing the materials of narrow pore size distributions with pore sizes over the range 2.8-6.8 nm, and specific surface areas up to 250 m 2/g. The analysis of pore structure was based on the comparison of nitrogen adsorption isotherms on a given porous sorbent and a standard nonporous polymer. Additionally the measurements of thermal stability and swelling of synthesized polymers were made. Adsorption of organic substances from aqueous solutions on porous polymers was also investigated.

  13. Slow flow in channels with porous walls

    CERN Document Server

    Jensen, Kaare H

    2012-01-01

    We consider the slow flow of a viscous incompressible liquid in a channel of constant but arbitrary cross section shape, driven by non-uniform suction or injection through the porous channel walls. A similarity transformation reduces the Navier-Stokes equations to a set of coupled equations for the velocity potential in two dimensions. When the channel aspect ratio and Reynolds number are both small, the problem reduces to solving the biharmonic equation with constant forcing in two dimensions. With the relevant boundary conditions, determining the velocity field in a porous channels is thus equivalent to solving for the vertical displacement of a simply suspended thin plate under uniform load. This allows us to provide analytic solutions for flow in porous channels whose cross-section is e.g. a rectangle or an equilateral triangle, and provides a general framework for the extension of Berman flow (Journal of Applied Physics 24(9), p. 1232, 1953) to three dimensions.

  14. Explosion propagation in inert porous media.

    Science.gov (United States)

    Ciccarelli, G

    2012-02-13

    Porous media are often used in flame arresters because of the high surface area to volume ratio that is required for flame quenching. However, if the flame is not quenched, the flow obstruction within the porous media can promote explosion escalation, which is a well-known phenomenon in obstacle-laden channels. There are many parallels between explosion propagation through porous media and obstacle-laden channels. In both cases, the obstructions play a duel role. On the one hand, the obstruction enhances explosion propagation through an early shear-driven turbulence production mechanism and then later by shock-flame interactions that occur from lead shock reflections. On the other hand, the presence of an obstruction can suppress explosion propagation through momentum and heat losses, which both impede the unburned gas flow and extract energy from the expanding combustion products. In obstacle-laden channels, there are well-defined propagation regimes that are easily distinguished by abrupt changes in velocity. In porous media, the propagation regimes are not as distinguishable. In porous media the entire flamefront is affected, and the effects of heat loss, turbulence and compressibility are smoothly blended over most of the propagation velocity range. At low subsonic propagation speeds, heat loss to the porous media dominates, whereas at higher supersonic speeds turbulence and compressibility are important. This blending of the important phenomena results in no clear transition in propagation mechanism that is characterized by an abrupt change in propagation velocity. This is especially true for propagation velocities above the speed of sound where many experiments performed with fuel-air mixtures show a smooth increase in the propagation velocity with mixture reactivity up to the theoretical detonation wave velocity. PMID:22213663

  15. Stabilization of a highly porous metal-organic framework utilizing a carborane-based linker.

    Science.gov (United States)

    Clingerman, Daniel J; Morris, William; Mondloch, Joseph E; Kennedy, Robert D; Sarjeant, Amy A; Stern, Charlotte; Hupp, Joseph T; Farha, Omar K; Mirkin, Chad A

    2015-04-18

    The first tritopic carborane-based linker, H3BCA (C15B24O6H30), based on closo-1,10-C2B8H10, has been synthesized and incorporated into a metal-organic framework (MOF), NU-700 (Cu3(BCA)2). In contrast to the analogous MOF-143, NU-700 can be activated with retention of porosity, yielding a BET surface area of 1870 m(2) g(-1). PMID:25767827

  16. Porous media fluid transport and pore structure

    CERN Document Server

    Dullien, F A L

    1992-01-01

    This book examines the relationship between transport properties and pore structure of porous material. Models of pore structure are presented with a discussion of how such models can be used to predict the transport properties of porous media. Portions of the book are devoted to interpretations of experimental results in this area and directions for future research. Practical applications are given where applicable, and are expected to be useful for a large number of different fields, including reservoir engineering, geology, hydrogeology, soil science, chemical process engineering, biomedica

  17. Porous ceramic scaffolds with complex architectures

    Energy Technology Data Exchange (ETDEWEB)

    Saiz, Eduardo; Munch, Etienne; Franco, Jaime; Deville, Sylvain; Hunger, Phillip; Saiz, Eduardo; Tomsia, Antoni P.

    2008-03-15

    This work compares two novel techniques for the fabrication of ceramic scaffolds for bone tissue engineering with complex porosity: robocasting and freeze casting. Both techniques are based on the preparation of concentrated ceramic suspensions with suitable properties for the process. In robocasting, the computer-guided deposition of the suspensions is used to build porous materials with designed three dimensional (3-D) geometries and microstructures. Freeze casting uses ice crystals as a template to form porous lamellar ceramic materials. Preliminary results on the compressive strengths of the materials are also reported.

  18. Transport of subsurface bacteria in porous media

    Energy Technology Data Exchange (ETDEWEB)

    Bales, R.C.; Arnold, R.G.; Gerba, C.P.

    1995-02-01

    The primary objective of this study was to develop tools with which to measure the advective transport of microorganisms through porous media. These tools were then applied to investigate the sorptive properties of representative microorganisms that were selected at random from the DOE`s deep subsurface collection of bacterial, maintained at Florida State University. The transport screening procedure that arose from this study was also used to investigate biological factors that affect the transport/sorption of biocolloids during their movement through porous media with the bulk advective flow.

  19. Novel hybrid multifunctional magnetoelectric porous composite films

    Science.gov (United States)

    Martins, P.; Gonçalves, R.; Lopes, A. C.; Venkata Ramana, E.; Mendiratta, S. K.; Lanceros-Mendez, S.

    2015-12-01

    Novel multifunctional porous films have been developed by the integration of magnetic CoFe2O4 (CFO) nanoparticles into poly(vinylidene fluoride)-Trifuoroethylene (P(VDF-TrFE)), taking advantage of the synergies of the magnetostrictive filler and the piezoelectric polymer. The porous films show a piezoelectric response with an effective d33 coefficient of -22 pC/N-1, a maximum magnetization of 12 emu g-1 and a maximum magnetoelectric coefficient of 9 mV cm-1 Oe-1. In this way, a multifunctional membrane has been developed suitable for advanced applications ranging from biomedical to water treatment.

  20. Heat transfers in porous media. Phase changes

    International Nuclear Information System (INIS)

    Phase change phenomena in porous media, like all poly-phase processes, are complex and still only partially understood. This article deals only with the liquid-vapor phase change (vaporization-condensation) because of its particular practical importance in numerous domains. Content: 1 - Fixing of a fluid constituent inside a porous matrix; 2 - mathematical modeling; 3 - example of reference situations: phase changes at temperatures below the saturation temperature (vaporization, condensation), phase changes at temperatures above the saturation temperature (condensation, vaporization-boiling); 4 - conclusion. (J.S.)

  1. Quasi-Porous Plug With Vortex Chamber

    Science.gov (United States)

    Walsh, J. V.

    1985-01-01

    Pressure-letdown valve combines quasi-porous-plug and vortex-chamber in one controllable unit. Valve useful in fossil-energy plants for reducing pressures in such erosive two-phase process streams as steam/water, coal slurries, or combustion gases with entrained particles. Quasi-Porous Plug consists of plenums separated by perforated plates. Number or size of perforations increases with each succeeding stage to compensate for expansion. In Vortex Chamber, control flow varies to control swirl and therefore difference between inlet and outlet pressures.

  2. Measurement of Emissivity of Porous Ceramic Materials

    OpenAIRE

    BÜYÜKALACA, Orhan

    1998-01-01

    In this study, measurements of spectral and total emissivities of seven different porous ceramic materials and one ceramic fibre material are reported. Measurements were made for wavelength range from 1.2 µm to 20 µm and temperature range from 200 °C to 700 °C. It was found that total emissivity increases with increase of pore size but decreases with increase of temperature. The results showed all the porous ceramic materials tested to be much better than ceramic fibre in terms of total em...

  3. Additive Manufacturing of Hierarchical Porous Structures

    Energy Technology Data Exchange (ETDEWEB)

    Grote, Christopher John [Los Alamos National Lab. (LANL), Los Alamos, NM (United States). Materials Science and Technology Division. Polymers and Coatings

    2016-08-30

    Additive manufacturing has become a tool of choice for the development of customizable components. Developments in this technology have led to a powerful array of printers that t serve a variety of needs. However, resin development plays a crucial role in leading the technology forward. This paper addresses the development and application of printing hierarchical porous structures. Beginning with the development of a porous scaffold, which can be functionalized with a variety of materials, and concluding with customized resins for metal, ceramic, and carbon structures.

  4. Mixed convection opposing flow in porous annulus

    Science.gov (United States)

    Salman, Ahmed N. J.; Kamangar, Sarfaraz; Al-Rashed, Abdullah A. A. A.; Khan, T. M. Yunus; Khaleed, H. M. T.

    2016-06-01

    The current work investigates the mixed convection flow in a vertical porous annulus embedded with fluid saturated porous medium. The annulus is isothermally heated discretely at 20%, 35% and 50% of the height of cylinder at the center of annulus. Darcy law with thermal non-equilibrium approach is considered. The governing partial differential equations are solved using Finite Element Method (FEM). The effects of Peclet number Pe and conductivity ratio Kr on heat transfer and fluid flow is discussed It is found that the applied velocity in the downward direction, in case of an opposing flow, does not allow the thermal energy to reach from a hot to a cold surface.

  5. Method to prepare nanoparticles on porous mediums

    Science.gov (United States)

    Vieth, Gabriel M [Knoxville, TN; Dudney, Nancy J [Oak Ridge, TN; Dai, Sheng [Knoxville, TN

    2010-08-10

    A method to prepare porous medium decorated with nanoparticles involves contacting a suspension of nanoparticles in an ionic liquid with a porous medium such that the particles diffuse into the pores of the medium followed by heating the resulting composition to a temperature equal to or greater than the thermal decomposition temperature of the ionic liquid resulting in the removal of the liquid portion of the suspension. The nanoparticles can be a metal, an alloy, or a metal compound. The resulting compositions can be used as catalysts, sensors, or separators.

  6. Computational study of porous materials for gas separations

    Science.gov (United States)

    Lin, Li-Chiang

    Nanoporous materials such as zeolites, zeolitic imidazolate frameworks (ZIFs), and metal-organic frameworks (MOFs) are used as sorbents or membranes for gas separations such as carbon dioxide capture, methane capture, paraffin/olefin separations, etc. The total number of nanoporous materials is large; by changing the chemical composition and/or the structural topologies we can envision an infinite number of possible materials. In practice one can synthesize and fully characterize only a small subset of these materials. Hence, computational study can play an important role by utilizing various techniques in molecular simulations as well as quantum chemical calculations to accelerate the search for optimal materials for various energy-related separations. Accordingly, several large-scale computational screenings of over one hundred thousand materials have been performed to find the best materials for carbon capture, methane capture, and ethane/ethene separation. These large-scale screenings identified a number of promising materials for different applications. Moreover, the analysis of these screening studies yielded insights into those molecular characteristics of a material that contribute to an optimal performance for a given application. These insights provided useful guidelines for future structural design and synthesis. For instance, one of the screening studies indicated that some zeolite structures can potentially reduce the energy penalty imposed on a coal-fired power plant by as much as 35% compared to the near-term MEA technology for carbon capture application. These optimal structures have topologies with a maximized density of pockets and they capture and release CO2 molecules with an optimal energy. These screening studies also pointed to some systems, for which conventional force fields were unable to make sufficiently reliable predictions of the adsorption isotherms of different gasses, e.g., CO2 in MOFs with open-metal sites. For these systems, we

  7. Review on Fractal Analysis of Porous Metal Materials

    OpenAIRE

    Wang, J. Z.; J. MA; Ao, Q. B.; H. Zhi; Tang, H. P.

    2015-01-01

    Porous metal materials are multifunctional lightweight materials and have been used widely in industry. The structural and functional characters of porous metal materials depend on the pore structure which can be described effectively by the fractal theory. This paper reviews the major achievements on fractal analysis of pore structure of porous metal materials made by State Key Laboratory of Porous Metal Materials, China, over the past few years. These include (i) designing and developing a ...

  8. Microfluidic devices and methods including porous polymer monoliths

    Science.gov (United States)

    Hatch, Anson V; Sommer, Gregory J; Singh, Anup K; Wang, Ying-Chih; Abhyankar, Vinay V

    2014-04-22

    Microfluidic devices and methods including porous polymer monoliths are described. Polymerization techniques may be used to generate porous polymer monoliths having pores defined by a liquid component of a fluid mixture. The fluid mixture may contain iniferters and the resulting porous polymer monolith may include surfaces terminated with iniferter species. Capture molecules may then be grafted to the monolith pores.

  9. Effects of Preparation on Luminescent Characterization of Porous Silicon

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Porous silicon samples are prepared by pulse electrochemical-etching and DC electrochemical-etching. The effects of different preparation methods on luminescent characterization of porous silicon are investigated. Compared with DC electrochemical-etching, pulse electrochemical-etching produces the porous silicon characterized by a more even surface, a stronger luminescence and a PL blue shift to a certain degree.

  10. MECHANICAL STRENGTH OF HIGHLY POROUS CERAMICS

    NARCIS (Netherlands)

    VANDENBORN, IC; SANTEN, A; HOEKSTRA, HD; DEHOSSON, JTM; Born, I.C. van den

    1991-01-01

    This paper reports on the mechanical strength of highly porous ceramics in terms of the Weibull and Duxbury-Leath distributions. More than 1000 side-crushing strength tests on silica-catalyst carriers of various particle sizes have been performed in series. Within a series, preparation conditions we

  11. Refractive index contrast in porous silicon multilayers

    Energy Technology Data Exchange (ETDEWEB)

    Nava, R.; Mora, M.B. de la; Tagueena-Martinez, J. [Centro de Investigacion en Energia, Universidad Nacional Autonoma de Mexico, Temixco, Morelos (Mexico); Rio, J.A. del [Centro de Investigacion en Energia, Universidad Nacional Autonoma de Mexico, Temixco, Morelos (Mexico); Centro Morelense de Innovacion y Transferencia Tecnologica, Consejo de Ciencia y Tecnologia del Estado de Morelos (Mexico)

    2009-07-15

    Two of the most important properties of a porous silicon multilayer for photonic applications are flat interfaces and a relative large refractive index contrast between layers in the optical wavelength range. In this work, we studied the effect of the current density and HF electrolyte concentration on the refractive index of porous silicon. With the purpose of increasing the refractive index contrast in a multilayer, the refractive index of porous silicon produced at low current was studied in detail. The current density applied to produce the low porosity layers was limited in order to keep the electrolyte flow through the multilayer structure and to avoid deformation of layer interfaces. We found that an electrolyte composed of hydrofluoric acid, ethanol and glycerin in a ratio of 3:7:1 gives a refractive index contrast around 1.3/2.8 at 600 nm. Several multilayer structures with this refractive index contrast were fabricated, such as dielectric Bragg mirrors and microcavities. Reflectance spectra of the structures show the photonic quality of porous silicon multilayers produced under these electrochemical conditions. (copyright 2009 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  12. Waveguide Prism Based on Porous Silicon

    Institute of Scientific and Technical Information of China (English)

    JIA Zhen-hong

    2004-01-01

    The fabrication of the oxidized porous silicon waveguide prism is reported by selectively electrochemical anodisation process. The direction changes of light beams in TE and TM polarization out of this waveguide prism were respectively measured,and the experimental results were analyzed.

  13. Pressure diffusion waves in porous media

    Energy Technology Data Exchange (ETDEWEB)

    Silin, Dmitry; Korneev, Valeri; Goloshubin, Gennady

    2003-04-08

    Pressure diffusion wave in porous rocks are under consideration. The pressure diffusion mechanism can provide an explanation of the high attenuation of low-frequency signals in fluid-saturated rocks. Both single and dual porosity models are considered. In either case, the attenuation coefficient is a function of the frequency.

  14. Size-effects in porous metals

    DEFF Research Database (Denmark)

    Niordson, Christian Frithiof; Tvergaard, Viggo

    The intrinsic size-effect for porous metals is investigated. The analyses are carried out numerically using a finite strain generalization of a higher order strain gradient plasticity model. Results for plane strain growth of cylindrical voids are presented in terms of response curves and curves...

  15. Adsorption Kinetics in Nanoscale Porous Coordination Polymers

    Energy Technology Data Exchange (ETDEWEB)

    Nune, Satish K.; Thallapally, Praveen K.; McGrail, Benard Peter; Annapureddy, Harsha V. R.; Dang, Liem X.; Mei, Donghai; Karri, Naveen; Alvine, Kyle J.; Olszta, Matthew J.; Arey, Bruce W.; Dohnalkova, Alice

    2015-10-07

    Nanoscale porous coordination polymers were synthesized using simple wet chemical method. The effect of various polymer surfactants on colloidal stability and shape selectivity was investigated. Our results suggest that the nanoparticles exhibited significantly improved adsorption kinetics compared to bulk crystals due to decreased diffusion path lengths and preferred crystal plane interaction.

  16. Chaotic Mixing in Three Dimensional Porous Media

    CERN Document Server

    Lester, Daniel R; Borgne, Tanguy Le

    2016-01-01

    Under steady flow conditions, the topological complexity inherent to all random 3D porous media imparts complicated flow and transport dynamics. It has been established that this complexity generates persistent chaotic advection via a three-dimensional (3D) fluid mechanical analogue of the baker's map which rapidly accelerates scalar mixing in the presence of molecular di?usion. Hence pore-scale fluid mixing is governed by the interplay between chaotic advection, molecular di?usion and the broad (power-law) distribution of fluid particle travel times which arise from the non-slip condition at pore walls. To understand and quantify mixing in 3D porous media, we consider these processes in a model 3D open porous network and develop a novel stretching continuous time random walk (CTRW) which provides analytic estimates of pore-scale mixing which compare well with direct numerical simulations. We ?nd that chaotic advection inherent to 3D porous media imparts scalar mixing which scales exponentially with longitudi...

  17. Porous Silicon—A Versatile Host Material

    Directory of Open Access Journals (Sweden)

    Klemens Rumpf

    2010-02-01

    Full Text Available This work reviews the use of porous silicon (PS as a nanomaterial which is extensively investigated and utilized for various applications, e.g., in the fields of optics, sensor technology and biomedicine. Furthermore the combination of PS with one or more materials which are also nanostructured due to their deposition within the porous matrix is discussed. Such nanocompounds offer a broad avenue of new and interesting properties depending on the kind of involved materials as well as on their morphology. The filling of the pores performed by electroless or electrochemical deposition is described, whereas different morphologies, reaching from micro- to macro pores are utilized as host material which can be self-organized or fabricated by prestructuring. For metal-deposition within the porous structures, both ferromagnetic and non-magnetic metals are used. Emphasis will be put on self-arranged mesoporous silicon, offering a quasi-regular pore arrangement, employed as template for filling with ferromagnetic metals. By varying the deposition parameters the precipitation of the metal structures within the pores can be tuned in geometry and spatial distribution leading to samples with desired magnetic properties. The correlation between morphology and magnetic behaviour of such semiconducting/magnetic systems will be determined. Porous silicon and its combination with a variety of filling materials leads to nanocomposites with specific physical properties caused by the nanometric size and give rise to a multiplicity of potential applications in spintronics, magnetic and magneto-optic devices, nutritional food additives as well as drug delivery.

  18. Surface States and Photoluminescence From Porous Silicon

    OpenAIRE

    Md. Nazrul Islam; Satyendra Kumar

    2011-01-01

    Photoluminescence (PL) spectra of freshly electrochemically etched porous silicon layers anodized under various condition have been measured and analyzed according to quantum confinement (QC) model and surface state models. The results support the combination of QC and surface state models for visible PL from fresh PS layers.

  19. Thermal and optical properties of porous silicon

    Directory of Open Access Journals (Sweden)

    Silva A. Ferreira da

    2001-01-01

    Full Text Available Thermal diffusivity and optical absorption have been investigated for porous silicon, at room temperature, using photoacoustic spectroscopy. The experimental results obtained conform well with the existing studies recently published. The value obtained for thermal diffusivity is 0.045 ± 0.002 cm²/s.The absorption onsets show energy structures, differing from the ordinary semiconductor of bulk type.

  20. Analazing the impact behavior of porous concrete

    NARCIS (Netherlands)

    Agar Ozbek, A.S.; Weerheijm, J.

    2014-01-01

    Porous concrete is a special type of cementitious material incorporating a high amount of meso-size air pores that makes its characteristics markedly different from normal concrete. Therefore, it is being investigated for various applications, aiming to benefit from the presence of the air voids in

  1. Zein Recovery Using Non-Porous Membranes

    Science.gov (United States)

    Mairal, Anurag P.; Ng, Alvin; Wijmans, Johannes G.

    2005-01-25

    A membrane process for treating zein solutions to increase the zein concentration in the solution. The process uses a non-porous membrane that preferentially permeates the solvent and rejects the zein. Optionally, the process can be operated as a diafiltration process to yield a concentrate of high zein purity.

  2. A porous SiC ammonia sensor

    NARCIS (Netherlands)

    Connolly, E.J.; Timmer, B.H.; Pham, H.T.M.; Groeneweg, J.; Sarro, P.M.; Olthuis, W.; French, P.J.

    2005-01-01

    When used as the dielectric in a capacitive sensing arrangement, porous SiC has been found to be extremely sensitive to the presence of ammonia (NH3) gas. The exact sensing method is still not clear, but NH3 levels as low as 0.5 ppm could be detected. We report the fabrication and preliminary charac

  3. Porous bead packings for gas chromatography

    Science.gov (United States)

    Pollock, G. E.; Woeller, F. H.

    1979-01-01

    Porous polyaromatic packing beads have low polarity, high efficiency, short retention time, and may be synthesized in size range of 50 to 150 micrometers (100 to 270 mesh). Mechanically strong beads may be produced using various materials depending on elements and compounds to be identified.

  4. Theory of porous media - past and present

    Energy Technology Data Exchange (ETDEWEB)

    Boer, R. de [Essen Univ. (Germany). Inst. fuer Mechanik

    1998-10-01

    Porous solids filled with liquid or gas play an important role in engineering, e.g., in material science, petroleum industry, chemical engineering, and soil mechanics as well as in biomechanics. Although porous media are of considerable practical significance the description of their mechanical and thermodynamical behavior has been unsatisfactory for a long time. The theory to describe the complex thermodynamical behavior of such saturated porous solids has come to certain well-founded conclusions only recently. It is the goal of this paper to show the historical development of the porous media theory, which already started in the eighteenth century, formed in some areas by polemic disputes and tragic events in the lifes of the scientists involved. Furthermore, the current state of the research into this subject is discussed, whereby the state of the development of the material independent basic equations and the constitutive theory is illustrated. For a certain class of models general theorems, such as minimum and maximum problems, are derived and the uniqueness of solutions of boundary value problems is proved. (orig.)

  5. Force modulation microscopy of multilayered porous silicon samples

    Science.gov (United States)

    Sbrana, F.; Ghulinyan, M.; Pavesi, L.

    2005-06-01

    In this paper we report on Force Modulation Microscopy (FMM) study and force-distance curve analysis of porous silicon layers grown on silicon. The characterization has been carried out on the cross section of porous silicon. The FMM images allowed us to investigate the morphological thickness of the layers through local elasticity differences resolving both between porous silicon layers of different porosities and between porous silicon and silicon itself. Force-distance curves showed different adhesion behaviour: porous silicon is more hydrophobic than bulk silicon in cross sectional view.

  6. Fluid flow and heat transfer in rotating porous media

    CERN Document Server

    Vadasz, Peter

    2016-01-01

    This Book concentrates the available knowledge on rotating fluid flow and heat transfer in porous media in one single reference. Dr. Vadasz develops the fundamental theory of rotating flow and heat transfer in porous media and introduces systematic classification and identification of the relevant problems. An initial distinction between rotating flows in isothermal heterogeneous porous systems and natural convection in homogeneous non-­‐isothermal porous systems provides the two major classes of problems to be considered. A few examples of solutions to selected problems are presented, highlighting the significant impact of rotation on the flow in porous media.

  7. Equilibrium and transfer in porous media 2 transfer laws

    CERN Document Server

    Daïan, Jean-François

    2014-01-01

    A porous medium is composed of a solid matrix and its geometrical complement: the pore space. This pore space can be occupied by one or more fluids. The understanding of transport phenomena in porous media is a challenging intellectual task.  This book provides a detailed analysis of the aspects required for the understanding of many experimental techniques in the field of porous media transport phenomena. It is aimed at studentsor engineers who may not be looking specifically to become theoreticians in porous media, but wish to integrate knowledge of porous media with their previous scientif

  8. Porous solid backbone impregnation for electrochemical energy conversion systems

    KAUST Repository

    Boulfrad, Samir

    2013-09-19

    An apparatus and method for impregnating a porous solid backbone. The apparatus may include a platform for holding a porous solid backbone, an ink jet nozzle configured to dispense a liquid solution onto the porous solid backbone, a positioning mechanism configured to position the ink jet nozzle proximate to a plurality of locations of the porous solid backbone, and a control unit configured to control the positioning mechanism to position the ink jet nozzle proximate to the plurality of locations and cause the ink jet nozzle to dispense the liquid solution onto the porous solid backbone.

  9. Combustion synthesis of porous titanium microspheres

    International Nuclear Information System (INIS)

    The synthesis of titanium porous microspheres by a combustion technique was studied under an argon atmosphere by using a TiO2 − 2.5Mg reactive mixture. The precursor, a fine TiO2 powder, was thermally treated in the range 600–1300 °C prior to the combustion experiments. TiO2 microspheres whose diameters were between 10 and 50 μm were obtained from precursor particles annealed in the range 900–1100 °C. A biphase product consisting of Ti and MgO phases was obtained when the TiO2 microspheres were reduced with Mg. The spherical morphology of the final particles was retained despite the relatively high combustion temperatures (1630–1670 °C) used in this study. Moreover, porous titanium microspheres were obtained when the MgO particles were dissolved using acid leaching. Scanning electron microscopy (SEM) images of the microspheres suggested that the spherical structure contained ∼0.5–2.0-μm-diameter porous windows. The Brunauer–Emmett–Teller (BET) surface area of the Ti microspheres was determined to be 2.8 m2 g−1. - Highlights: • TiO2 + 2.5Mg mixture was combusted under argon pressure to produce titanium microspheres. • Microspheres with a porous framework structure were obtained at 1630–1670 °C. • The microspheres exhibited 10–50 μm average diameters with porous window of ∼0.5–2.0 μm and BET surface area of 2.8 m2 g−1. - Graphical abstract: Display Omitted

  10. Hydrogen storage by physisorption on porous materials

    Energy Technology Data Exchange (ETDEWEB)

    Panella, B.

    2006-09-13

    A great challenge for commercializing hydrogen powered vehicles is on-board hydrogen storage using economic and secure systems. A possible solution is hydrogen storage in light-weight solid materials. Here three principle storage mechanisms can be distinguished: i) absorption of hydrogen in metals ii) formation of compounds with ionic character, like complex hydrides and iii) physisorption (or physical adsorption) of hydrogen molecules on porous materials. Physical adsorption exhibits several advantages over chemical hydrogen storage as for example the complete reversibility and the fast kinetics. Two classes of porous materials were investigated for physical hydrogen storage, i.e. different carbon nanostructures and crystalline metal-organic frameworks possessing extremely high specific surface area. Hydrogen adsorption isotherms were measured using a Sieverts' apparatus both at room temperature and at 77 K at pressures up to the saturation regime. Additionally, the adsorption sites of hydrogen in these porous materials were identified using thermal desorption spectroscopy extended to very low temperatures (down to 20 K). Furthermore, the adsorbed hydrogen phase was studied in various materials using Raman spectroscopy at different pressures and temperatures. The results show that the maximum hydrogen storage capacity of porous materials correlates linearly with the specific surface area and is independent of structure and composition. In addition the pore structure of the adsorbent plays an important role for hydrogen storage since the adsorption sites for H2 could be assigned to pores possessing different dimensions. Accordingly it was shown that small pores are necessary to reach high storage capacities already at low pressures. This new understanding may help to tailor and optimize new porous materials for hydrogen storage. (orig.)

  11. Increasing the CO2 /N2 Selectivity with a Higher Surface Density of Pyridinic Lewis Basic Sites in Porous Carbon Derived from a Pyridyl-Ligand-Based Metal-Organic Framework.

    Science.gov (United States)

    Li, Liangjun; Wang, Ying; Gu, Xin; Yang, Qipeng; Zhao, Xuebo

    2016-07-01

    The development of functional porous carbon with high CO2 /N2 selectivity is of great importance for CO2 capture. In this paper, a type of porous carbon with doped pyridinic sites (termed MOFC) was prepared from the carbonization of a pyridyl-ligand based MOF. Four MOFCs derived from different carbonizing temperatures were prepared. Structural studies revealed high contents of pyridinic-N groups and nearly the same pore-size distributions for these MOFCs. Gas-sorption studies revealed outstanding CO2 uptake at low pressures and room temperature. Owing to the high content of pyridinic-N groups, the CO2 /N2 selectivity on these MOFCs exhibits values of about 40-50, which are among the top values in carbon materials. Further correlation studies demonstrated that the CO2 /N2 selectivities show a positive linear relationship with the surface density of pyridinic-N groups, thus validating the synergistic effect of the doped pyridinic-N groups on CO2 adsorption selectivity. PMID:27146096

  12. Nanoporous cobalt(II) MOF exhibiting four magnetic ground states and changes in gas sorption upon post-synthetic modification.

    Science.gov (United States)

    Zeng, Ming-Hua; Yin, Zheng; Tan, Yan-Xi; Zhang, Wei-Xiong; He, Yan-Ping; Kurmoo, Mohamedally

    2014-03-26

    We present the syntheses, structural characterization, gas sorption, I2 uptake, and magnetic properties of a double-walled porous metal-organic framework, [Co(II)3(lac)2(pybz)2]·3DMF (1·3DMF, purple, where pybz = 4-pyridyl benzoate, lac = d- and l-lactate) and of its post-synthetic modified (PSM) congeners, [Co(II)3(lac)2(pybz)2]·xGuest (xGuest = 6MeOH, purple; 4.5EtOH, purple; 3PrOH, purple; 2C6H6, purple; 2.7I2, black), [Co(II)3(lac)2(pybz)2] (1, purple), [Co(II)3(pybz)2(lac)2(H2O)2]·7H2O (1a·7H2O, green), and [Co(III)Co(II)2(pybz)2(lac)2(H2O)2]I·2H2O·1.5DMSO (1b·I(-)·2H2O·1.5DMSO, yellow, DMSO = dimethyl sulfoxide). Crystallography shows that the framework is not altered by the replacement of DMF by different solvents or by the removal of the solvent molecules during the single-crystal to single-crystal (SC-SC) transformations, while upon exchange with H2O or partial oxidation by molecular iodine, the crystallinity is affected. 1 absorbs N2, H2, CH4, CH3OH, C2H5OH, PrOH, C6H6, and I2, but once it is in contact with H2O the absorption efficiency is drastically reduced. Upon PSM, the magnetism is transformed from a canted antiferromagnet (1·3DMF and 1·xGuest) to single-chain magnet (1), to a ferrimagnet (1a·7H2O), and to a ferromagnet (1b·I(-)·2H2O·1.5DMSO). Raman spectroscopy suggests the color change (purple to green 1a·7H2O or yellow 1b·I(-)·2H2O·1.5DMSO) is associated with a change of geometry from a strained octahedron due to the very acute chelating angle (∼60°) of the lactate of a cobalt center to a regular octahedron with a monodentate carboxylate and one H2O. The magnetic transformation is explained by the different interchain exchanges (J'), antiferromagnetic for 1·3DMF and 1·xSolvent (J' 0), between homometal topological ferrimagnetic chains (two octahedral and one tetrahedral Co(II) ions) connected by the double walls of pybz at 13.3 Å (shortest Co···Co). For 1b·I(-)·2H2O·1.5DMSO the moment of the tetrahedral site is

  13. The first example of commensurate adsorption of atomic gas in a MOF and effective separation of xenon from other noble gases

    KAUST Repository

    Wang, Hao

    2014-01-01

    In industry, cryogenic rectification for separating xenon from other noble gases such as krypton and argon is an energy and capital intensive process. Here we show that a microporous metal-organic framework, namely Co 3(HCOO)6 is capable of effective capture and separation of xenon from other noble gases. Henry\\'s constant, isosteric heat of adsorption (Qst), and IAST selectivity are calculated based on single component sorption isotherms. Having the highest Qst reported to date, Co 3(HCOO)6 demonstrates high adsorption capacity for xenon and its IAST selectivity for Xe-Kr is the largest among all MOFs investigated to date. To mimic real world conditions, breakthrough experiments are conducted on Xe-Kr binary mixtures at room temperature and 1 atmosphere. The results are consistent with the calculated data. These findings show that Co 3(HCOO)6 is a promising candidate for xenon capture and purification. Our gas adsorption measurements and molecular simulation study also reveal that the adsorption of xenon represents the first example of commensurate adsorption of atomic gases near ambient conditions. © 2014 The Royal Society of Chemistry.

  14. N-doped graphene layers encapsulated NiFe alloy nanoparticles derived from MOFs with superior electrochemical performance for oxygen evolution reaction

    Science.gov (United States)

    Feng, Yi; Yu, Xin-Yao; Paik, Ungyu

    2016-01-01

    Water splitting, an efficient approach for hydrogen production, is often hindered by unfavorable kinetics of oxygen evolution reaction (OER). In order to reduce the overpotential, noble metal oxides-based electrocatalysts like RuO2 and IrO2 are usually utilized. However, due to their scarcity, the development of cost-effective non-precious OER electrocatalysts with high efficiency and good stability is urgently required. Herein, we report a facile one-step annealing of metal-organic frameworks (MOFs) strategy to synthesize N-doped graphene layers encapsulated NiFe alloy nanoparticles (NiFe@C). Through tuning the nanoparticle size and calcination temperature, NiFe@C with an average size of around 16 nm obtained at 700 °C exhibits superior OER performance with an overpotential of only 281 mV at 10 mA cm−2 and high durability. The facile synthesis method and excellent electrochemical performance show great potential of NiFe@C in replacing the precious metal-based electrocatalysts in the OER. PMID:27658968

  15. The formation of the Baptistina family by catastrophic disruption: Porous versus non-porous parent body

    Science.gov (United States)

    Jutzi, M.; Michel, P.; Benz, W.; Richardson, D. C.

    2009-01-01

    In this paper, we present numerical simulations aimed at reproducing the Baptistina family based on its properties estimated by observations. A previous study by Bottke et al. (2007) indicated that this family is probably at the origin of the K/T impactor, is linked to the CM meteorites and was produced by the disruption of a parent body 170 km in size due to the head-on impact of a projectile 60 km in size at 3 km s-1. This estimate was based on simulations of fragmentation of non-porous materials, while the family was assumed to be of C taxonomic type, which is generally interpreted as being formed from a porous body. Using both a model of fragmentation of non-porous materials, and a model that we developed recently for porous ones, we performed numerical simulations of disruptions aimed at reproducing this family and at analyzing the differences in the outcome between those two models. Our results show that a reasonable match to the estimated size distribution of the real family is produced from the disruption of a porous parent body by the head-on impact of a projectile 54 km in size at 3 km s-1. Thus, our simulations with a model consistent with the assumed dark type of the family requires a smaller projectile than previously estimated, but the difference remains small enough to not affect the proposed scenario of this family history. We then find that the break-up of a porous body leads to different outcomes than the disruption of a non-porous one. The real properties of the Baptistina family still contain large uncertainties, and it remains possible that its formation did not involve the proposed impact conditions. However, the simulations presented here already show some range of outcomes and once the real properties are better constrained, it will be easy to check whether one of them provides a good match.

  16. Permeability equipment for porous friction surfaces

    Science.gov (United States)

    Standiford, D. L.; Graul, R. A.; Lenke, L. R.

    1985-04-01

    Hydroplaning is the loss of traction between tires and pavement due to the presence of a layer of water. This loss of traction can result in loss of vehicle control. A porous friction surface (PFS) applied over an existing pavement permits the water to drain laterally and vertically away from the tire path, effectively lowering hydroplaning potential. Equipment used to measure pavement drainage (permeability) is discussed with respect to usage on porous friction surface. Background information on hydroplaning, flow theory, and PFS field performance as they are affected by permeability are also presented. Two dynamic test devices and four static devices are considered for measuring PFS permeability. Permeability tests are recommended to measure PFS permeability for maintenance purposes and construction control. Dynamic devices cited could possibly estimate hydroplaning potential; further research must be done to determine this. Permeability devices cannot be used to accurately estimate friction of a pavement surface, however, decreased permeability of a pavement infers a decrease in friction.

  17. Uniaxial deformation of a soft porous material

    Science.gov (United States)

    MacMinn, Chris; Dufresne, Eric; Wettlaufer, John

    2015-11-01

    Compressing a porous material will decrease the volume of pore space, driving fluid out. Similarly, injecting fluid into a porous material will drive mechanical deformation, distorting the solid skeleton. This poromechanical coupling has applications ranging from cell and tissue mechanics to geomechanics and hydrogeology. The classical theory of linear poroelasticity captures this coupling by combining Darcy's law with linear elasticity and then further linearizing in the strain. This is a good model for very small deformations, but it becomes increasingly inappropriate as deformations grow larger, and moderate to large deformations are common in the context of phenomena such as swelling, damage, and extreme softness. Here, we compare the predictions of linear poroelasticity with those of a rigorous large-deformation framework in the context of two uniaxial model problems. We explore the error associated with the linear model in both steady and dynamic situations, as well as the impact of allowing the permeability to vary with the deformation.

  18. Magnetohydrodynamic Flow Between Concentric Rotating Porous Cylinders

    Directory of Open Access Journals (Sweden)

    S. N. Dube

    1971-10-01

    Full Text Available An attempt has been made to study the steady laminar flow of a incompressible electrically conducting fluid between infinitely long concentric rotating porous cylinders under the influence of radial magnetic field. A solution has been obtained under the assumption of uniform conditions along the axis of the cylinders. The cylinders being porous, a hyperbolic radial velocity distribution has been superimposed over the circumferential velocity produced due to rotation. There is a Bernoulli type pressure variation in the radial in the direction. When the inner cylinder is at rest the shearing stress at it and the torque transmitted to it decrease as R (=v/Sub/1y/Sub1/v= v/Sub2y/Sub2/v increases and the magnetic parameter lambda (=4sigma mue/sube/sup2A/Sup2/Mue will further decrease them.

  19. Wave Interaction with Porous Coastal Structures

    DEFF Research Database (Denmark)

    Jensen, Bjarne

    of structures are rubble mound breakwaters and berm breakwaters where common structural elements are core material, filter layers and armour layers. The armour stones serves as the main protection of the filter and core material against wave action. Therefore the armour stones must maintain stable when exposed...... are also applied as part of investigating and designing breakwaters. The models can provide more detailed information on some topics, such as pressure attenuation through the porous core material, while it is more difficult to simulate the direct destabilisation and movements of individual stones...... the contribution to generation of turbulence, and destabilizing shear stresses, from the wave breaking, the armour layer, and the porous core was singled out. In Chapter 3 a similar detailed approach was taken towards experimental investigation of the pressure induced forces in the filter layers below the main...

  20. Porous graphene materials for water remediation.

    Science.gov (United States)

    Niu, Zhiqiang; Liu, Lili; Zhang, Li; Chen, Xiaodong

    2014-09-10

    Water remediation has been a critical issue over the past decades due to the expansion of wastewater discharge to the environment. Currently, a variety of functional materials have been successfully prepared for water remediation applications. Among them, graphene is an attractive candidate due to its high specific surface area, tunable surface behavior, and high strength. This Concept paper summarizes the design strategy of porous graphene materials and their applications in water remediation, such as the cleanup of oil, removal of heavy metal ions, and elimination of water soluble organic contaminants. The progress made so far will guide further development in structure design strategy of porous materials based on graphene and exploration of such materials in environmental remediation.

  1. Porous media: Analysis, reconstruction and percolation

    DEFF Research Database (Denmark)

    Rogon, Thomas Alexander

    1995-01-01

    been determined. We have obtained results which indicate that the effect of spatial correlation does affect not only the percolation threshold but also the exponents with respect to the values known for random media. We have attempted to predict key percolation values for a continuous medium (i......Spatial structure of selected porous media has been analysed in terms of the two first spatial moments (i.e. porosity and autocorrelation). Having established directional isotropy in the three spatial planes, multiple geometrical features measured in 2-d are attempted generalized to 3-d using...... in binary fields. Percolation threshold of reconstructed porous media has been determined for different discretizations of a selected model correlation function. Also critical exponents such as the correlation length exponent v, the strength of the infinite network and the mean size of finite clusters have...

  2. Unreacted Hugoniots for porous and liquid explosives

    Energy Technology Data Exchange (ETDEWEB)

    Gustavsen, R.L.; Sheffield, S.A.

    1993-08-01

    Numerous authors have measured the Hugoniots of a variety of granular explosives pressed to different densities. Each explosive at each density was typically then treated as a unique material having its own Hugoniot. By combining methods used by Hayes, Sheffield and Mitchell (for describing the Hugoniot of HNS at various densities) with Hermann`s P-{alpha} model, it is only necessary to know some thermodynamic constants or the Hugoniot of the initially solid material and the porous material sound speed to obtain accurate unreacted Hugoniots for the porous explosive. We discuss application of this method to several materials including HMX, PETN, TNT, and Tetryl, as well as HNS. We also show that the ``Universal Liquid Hugoniot`` can be used to calculate the unreacted Hugoniot for liquid explosives. With this method only the ambient pressure sound speed and density are needed to predict the Hugoniot. Applications presented include nitromethane and liquid TNT.

  3. Ultimate permeation across atomically thin porous graphene.

    Science.gov (United States)

    Celebi, Kemal; Buchheim, Jakob; Wyss, Roman M; Droudian, Amirhossein; Gasser, Patrick; Shorubalko, Ivan; Kye, Jeong-Il; Lee, Changho; Park, Hyung Gyu

    2014-04-18

    A two-dimensional (2D) porous layer can make an ideal membrane for separation of chemical mixtures because its infinitesimal thickness promises ultimate permeation. Graphene--with great mechanical strength, chemical stability, and inherent impermeability--offers a unique 2D system with which to realize this membrane and study the mass transport, if perforated precisely. We report highly efficient mass transfer across physically perforated double-layer graphene, having up to a few million pores with narrowly distributed diameters between less than 10 nanometers and 1 micrometer. The measured transport rates are in agreement with predictions of 2D transport theories. Attributed to its atomic thicknesses, these porous graphene membranes show permeances of gas, liquid, and water vapor far in excess of those shown by finite-thickness membranes, highlighting the ultimate permeation these 2D membranes can provide. PMID:24744372

  4. Large deformations of a soft porous material

    CERN Document Server

    MacMinn, Christopher W; Wettlaufer, John S

    2015-01-01

    Compressing a porous material will decrease the volume of pore space, driving fluid out. Similarly, injecting fluid into a porous material can drive mechanical deformation, distorting the solid skeleton. This poromechanical coupling has applications ranging from cell and tissue mechanics to geomechanics and hydrogeology. The classical theory of linear poroelasticity captures this coupling by combining Darcy's law with linear elasticity and then further linearizing in the strain. This is a good model for very small deformations, but it becomes increasingly inappropriate as deformations grow larger, and moderate to large deformations are common in the context of phenomena such as swelling or damage, or for materials that are extremely soft. Here, we first review a rigorous Eulerian framework for large-deformation poromechanics. We then compare the predictions of linear poroelasticity with those of fully nonlinear poromechanics in the context of two uniaxial model problems: Fluid outflow driven by an applied mec...

  5. Investigation of drug-porous adsorbent interactions in drug mixtures with selected porous adsorbents.

    Science.gov (United States)

    Madieh, Shadi; Simone, Michael; Wilson, Wendy; Mehra, Dev; Augsburger, Larry

    2007-04-01

    The adsorption of drugs onto porous substrates may prove to be a convenient method by which to enhance the dissolution rate of certain poorly water-soluble drugs in body fluids. The purpose of this research is to provide a better understanding of the type of interactions occurring between drugs and certain pharmaceutically acceptable porous adsorbents that leads to enhanced drug dissolution rates. The interactions between ibuprofen (acidic drug), acetaminophen (acidic drug), dipyridamole (basic drug), and the porous adsorbents used (calcium silicate and silica gel) were investigated using differential scanning calorimetry (DSC), powder X-ray diffraction (PXRD), and Fourier Transform infrared spectroscopy (FTIR). DSC and PXRD results indicated a significant loss of crystallinity of both ibuprofen and acetaminophen but not dipyridamole. In the case of ibuprofen, FTIR results indicated the ionization of the carboxylic group based on the shift in the FTIR carboxylic band. Dissolution of ibuprofen from its mixtures with porous adsorbents was found to be significantly higher compared to the neat drug, whereas dipyridamole dissolution from its mixtures with porous adsorbents was not significantly different from that of the neat drug. PMID:17221849

  6. FACADE SYSTEM MADE OF POROUS MATERIALS

    Directory of Open Access Journals (Sweden)

    Zhukov Aleksey Dmitrievich

    2012-10-01

    Full Text Available The proposed multi-component façade system is made of porous concretes employed both as bearing structures and for heat insulation and fireproofing purposes. The authors also provide their recommendations in respect of the mounting of the proposed façade system. The façade system considered in the article is composed of wall foam concrete blocks reinforced by basalt fibers (bearing elements of the structure, cellular concrete polystyrene (thermal insulation, and porous concrete (fireproofing and thermal insulation. Retained shuttering (in the fireproofing sections represents chrysolite cement sheets attached to the structures composed of glass-fiber plastic elements. The application of insulating porous concrete as a fireproofing material is based on the principle of adjustable stress-strained states of materials in the environment of variable pressure. This technology was developed at Moscow State University of Civil Engineering, and it was initially designated for the manufacturing of tailor-made products. The above concrete is also designated for retained shuttering and modified cavity masonry walls. Porous concrete that expands inside the fireproofing cavity ensures a tight contact both with the basic material and thermal insulation plates. The use of materials of the same origin (Portland cement means the formation of strong transition zones connecting the system components in the course of its hardening and further operation. The results of the thermotechnical calculation demonstrate that the thermal resistance registered on the surface of the wall that is 3 meters high (that has a 0.4 m fireproofing cavity is equal to 3.98 sq. m. C/Wt. The value of the coefficient of thermotechnical heterogeneity (r is equal to 0.86 with account for the thickness and thermal conductivity of point and linear elements. If the thermotechnical heterogeneity is taken into consideration, the thermal resistance of the proposed wall is equal to 3.42 m2 С/Wt.

  7. Magnetic Fluid Flows in Porous Media

    Institute of Scientific and Technical Information of China (English)

    LI Ming-Jun; CHEN Liang

    2011-01-01

    @@ The seepage law under a magnetic field is obtained by up-scaling the flow at the pore scale of rigid porous media,and the macroscopic equivalent model is also obtained.It is proved that the macroscopic mass flow depends on the macroscopic magnetic force and the gradients of pressure and of magnetic pressure, as Zahn and Rosensweig have described in their experiments.The permeability tensor is symmetric and positive.

  8. Extending the Lifespan of Porous Asphalt Concrete

    OpenAIRE

    Zhang, Y.

    2015-01-01

    Porous Asphalt (PA) concrete is widely used as a surfacing layer on highways in the Netherlands. The service life of PA wearing courses is limited because of the fact that it is vulnerable to raveling. The possibilities of applying preventive maintenance to PA wearing courses by means of spraying rejuvenation products on the pavement surfaces are being investigated with high interest in the Netherlands. A material which has the ability to penetrate into the bituminous binder and soften (rejuv...

  9. Ultraviolet photoluminescence of porous anodic alumina films

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    Photoluminescence (PL) properties of porous anodic alumina (PAA) films prepared by using electrochemical anodization technique in a mixed solution of oxalic and sulfuric acid have been investigated. The PAA films have an intensive ultraviolet PL emission around 350 nm, of which a possible PL mechanism has been proposed. It was found that the incorporated oxalic ions, which could transform into PL centers and exist in the PAA films, are responsible for this ultraviolet PL emission.

  10. Increased Functionality Porous Optical Fiber Structures

    OpenAIRE

    Wooddell, Michael Gary

    2007-01-01

    A novel fiber optic structure, termed stochastic ordered hole fibers, has been developed that contains an ordered array of six hollow tubes surrounding a hollow core, combined with a nanoporous glass creating a unique fully three dimensional pore/fiber configuration. The objective of this study is to increase the functionality of these stochastic ordered hole fibers, as well as porous clad fibers, by integrating electronic device components such as conductors, and semiconductor...

  11. Porous hydroxyapatite for artificial bone applications

    OpenAIRE

    I. Sopyan et al

    2007-01-01

    Hydroxyapatite (HA) has been used clinically for many years. It has good biocompatibility in bone contact as its chemical composition is similar to that of bone material. Porous HA ceramics have found enormous use in biomedical applications including bone tissue regeneration, cell proliferation, and drug delivery. In bone tissue engineering it has been applied as filling material for bone defects and augmentation, artificial bone graft material, and prosthesis revision surgery. Its high surfa...

  12. Wave propagation in fractured porous media

    OpenAIRE

    Tuncay, Kağan; Çorapçıoplu, M. Yavuz

    1996-01-01

    A theory of wave propagation in fractured porous media is presented based on the double-porosity concept. The macroscopic constitutive relations and mass and momentum balance equations are obtained by volume averaging the microscale balance and constitutive equations and assuming small deformations. In microscale, the grains are assumed to be linearly elastic and the fluids are Newtonian. Momentum transfer terms are expressed in terms of intrinsic and relative permeabilities assuming the vali...

  13. Finite volume hydromechanical simulation in porous media

    OpenAIRE

    Nordbotten, Jan Martin

    2014-01-01

    Cell-centered finite volume methods are prevailing in numerical simulation of flow in porous media. However, due to the lack of cell-centered finite volume methods for mechanics, coupled flow and deformation is usually treated either by coupled finite-volume-finite element discretizations, or within a finite element setting. The former approach is unfavorable as it introduces two separate grid structures, while the latter approach loses the advantages of finite volume methods for the flow equ...

  14. Preparation of porous materials for radionuclides capture

    International Nuclear Information System (INIS)

    Porous materials showing promise for radionuclide capture from water at contaminated sites were prepared. Nanoporous materials (size of pores 1-100 nm) and some polymers are well suited to this purpose owing their affinity for selected radionuclides. Nanoporous metal oxides and silica gel with styrene-divinylbenzene-TODGA-modified surface were prepared, characterized and tested for radionuclide (227Ac, 227Th, 223Ra) capture efficiency. (orig.)

  15. Size-effects in porous metals

    DEFF Research Database (Denmark)

    Niordson, Christian Frithiof; Tvergaard, Viggo

    2007-01-01

    of the material. For porous materials with small void volume fractions under highly triaxial tension, void growth is analysed through cavitation instabilities using a finite element Rayleigh–Ritz procedure. Cavitation instabilities are found to be delayed for small voids, so that higher stress levels are needed...... in order to obtain unstable growth. Cavitation diagrams for cylindrical voids are compared with cavitation diagrams for axi-symmetric void growth of initially spherical voids....

  16. Methane storage in porous activated carbons

    OpenAIRE

    Perl, András; Gemert, Wim van

    2014-01-01

    Locally produced methane, - either as biomethane or power-to-gas product, has to be stored to provide a reliable gas source for the fluctuating demand of any local gas distribution network. Additionally, methane is a prominent transportation fuel but its suitability for vehicular application depends on the ability to store an adequate amount in the onboard fuel tank. Adsorption in porous materials could enable a simple, safe and cost-effective method for storing methane at ambient temperature...

  17. Porous concrete mixtures for pervious urban pavements

    OpenAIRE

    Castro, J.; Fernández, B.; Videla, C.; de Solminihac, H.

    2007-01-01

    The present study aimed to analyze the hydraulic and mechanical behaviour of a series of roller-compacted, laboratory porous concrete mixtures. The mix design variables examined were the actual void ratio in the hardened concrete and the water/cement ratio. From these results the better dosages from the mechanical and hydraulical behaviour point of view were determined. One of the designs developed was found to exhibit excellent hydraulic capacity and 20% greater strength than the mixtures re...

  18. Superfluid Helium Flow in Porous Media

    OpenAIRE

    Allain, Hervé; Quintard, Michel; Soulaine, Cyprien; Prat, Marc; Baudouy, Bertrand; Van Weelderen, Rob

    2013-01-01

    Superfluid helium is primarily used in the field of applied superconductivity. Given the complexity of the magnet geometry and the scales involved, a real 3D simulation of heat transfer in such devices at the micro-channel scale is very difficult, even impossible. However, the repeatability or even periodicity of the structure suggests the possibility of a macro-scale description following a porous medium approach. Which macro-scale model may be used? This largely remains an open field while ...

  19. Porous Organic Polymers for CO2 Capture

    KAUST Repository

    Teng, Baiyang

    2013-05-01

    Carbon dioxide (CO2) has long been regarded as the major greenhouse gas, which leads to numerous negative effects on global environment. The capture and separation of CO2 by selective adsorption using porous materials proves to be an effective way to reduce the emission of CO2 to atmosphere. Porous organic polymers (POPs) are promising candidates for this application due to their readily tunable textual properties and surface functionalities. The objective of this thesis work is to develop new POPs with high CO2 adsorption capacities and CO2/N2 selectivities for post-combustion effluent (e.g. flue gas) treatment. We will also exploit the correlation between the CO2 capture performance of POPs and their textual properties/functionalities. Chapters Two focuses on the study of a group of porous phenolic-aldehyde polymers (PPAPs) synthesized by a catalyst-free method, the CO2 capture capacities of these PPAPs exceed 2.0 mmol/g at 298 K and 1 bar, while keeping CO2/N2 selectivity of more than 30 at the same time. Chapter Three reports the gas adsorption results of different hyper-cross-linked polymers (HCPs), which indicate that heterocyclo aromatic monomers can greatly enhance polymers’ CO2/N2 selectivities, and the N-H bond is proved to the active CO2 adsorption center in the N-contained (e.g. pyrrole) HCPs, which possess the highest selectivities of more than 40 at 273 K when compared with other HCPs. Chapter Four emphasizes on the chemical modification of a new designed polymer of intrinsic microporosity (PIM) with high CO2/N2 selectivity (50 at 273 K), whose experimental repeatability and chemical stability prove excellent. In Chapter Five, we demonstrate an improvement of both CO2 capture capacity and CO2/N2 selectivity by doping alkali metal ions into azo-polymers, which leads a promising method to the design of new porous organic polymers.

  20. Synthesis of Ti-Al porous perform

    Directory of Open Access Journals (Sweden)

    K. Naplocha

    2008-02-01

    Full Text Available Purpose: Article describes production method of intermetallic porous perform for reinforcing of composite materials. Usefulness of the high temperature self-propagating synthesis (SHS, with appropriate modification, to produce perform for production of composite was evaluated.Design/methodology/approach: Mixture of aluminum and titanium powder was cold isostatically pressed (CIPed and produced cylindrical pill was ignited in microwave field. Obtained structure usually have open porosity what enables for pressure infiltration with molten metal. The investigations of the structure of preforms on the scanning electron microscope (SEM were made.Findings: The produced performs in most cases reveal open porosity, uniform morphology and are suitable for infiltration process. After reaction Al-Ti compounds form partly globular structure with microhardness much higher than substratesResearch limitations/implications: In the actual stages of this work proposed method can be used for manufacturing of porous performs, which mainly contain Al3Ti. During reaction, mixture compacts with the molar ratio of Al/Ti=1 were transformed into inhomogeneous structure.Practical implications: Obtained perform can be widely used as the reinforcement to produce hybrid composite materials by the infiltration method. Aluminum casting alloys can be locally reinforced to improve hardness and resistance to oxidization at high temperature.Originality/value: Article is valuable for persons engaged in production of casting composite materials reinforced with porous perform. Proposed method allows to incorporate hard structures from Al-Ti compounds into aluminum casting.

  1. Streaming potential near a rotating porous disk.

    Science.gov (United States)

    Prieve, Dennis C; Sides, Paul J

    2014-09-23

    Theory and experimental results for the streaming potential measured in the vicinity of a rotating porous disk-shaped sample are described. Rotation of the sample on its axis draws liquid into its face and casts it from the periphery. Advection within the sample engenders streaming current and streaming potential that are proportional to the zeta potential and the disk's major dimensions. When Darcy's law applies, the streaming potential is proportional to the square of the rotation at low rate but becomes invariant with rotation at high rate. The streaming potential is invariant with the sample's permeability at low rate and is proportional to the inverse square of the permeability at high rate. These predictions were tested by determining the zeta potential and permeability of the loop side of Velcro, a sample otherwise difficult to characterize; reasonable values of -56 mV for zeta and 8.7 × 10(-9) m(2) for the permeability were obtained. This approach offers the ability to determine both the zeta potential and the permeability of materials having open structures. Compressing them into a porous plug is unnecessary. As part of the development of the theory, a convenient formula for a flow-weighted volume-averaged space-charge density of the porous medium, -εζ/k, was obtained, where ε is the permittivity, ζ is the zeta potential, and k is the Darcy permeability. The formula is correct when Smoluchowski's equation and Darcy's law are both valid.

  2. Porous photonic crystal external cavity laser biosensor

    Science.gov (United States)

    Huang, Qinglan; Peh, Jessie; Hergenrother, Paul J.; Cunningham, Brian T.

    2016-08-01

    We report the design, fabrication, and testing of a photonic crystal (PC) biosensor structure that incorporates a porous high refractive index TiO2 dielectric film that enables immobilization of capture proteins within an enhanced surface-area volume that spatially overlaps with the regions of resonant electromagnetic fields where biomolecular binding can produce the greatest shifts in photonic crystal resonant wavelength. Despite the nanoscale porosity of the sensor structure, the PC slab exhibits narrowband and high efficiency resonant reflection, enabling the structure to serve as a wavelength-tunable element of an external cavity laser. In the context of sensing small molecule interactions with much larger immobilized proteins, we demonstrate that the porous structure provides 3.7× larger biosensor signals than an equivalent nonporous structure, while the external cavity laser (ECL) detection method provides capability for sensing picometer-scale shifts in the PC resonant wavelength caused by small molecule binding. The porous ECL achieves a record high figure of merit for label-free optical biosensors.

  3. Dynamics of clogging in drying porous media

    Science.gov (United States)

    Kaplan, C. Nadir; Mahadevan, L.

    2014-11-01

    Drying in porous media pervades a range of phenomena from brine evaporation arrested in porous bricks, causing efflorescence, i.e. salt aggregation on the surface where vapor leaves the medium, to clogging of reservoir rocks via salt precipitation when carbon dioxide is injected for geological storage. During the process of drying, the permeability and porosity of the medium may change due to the solute accumulation as a function of the particle concentration, in turn affecting the evaporation rate and the dynamics of the fluid flow imposed by it. To examine the dynamics of these coupled quantities, we develop a multiphase model of the particulate flow of a saline suspension in a porous medium, induced by evaporation. We further provide dimensional arguments as to how the salt concentration and the resulting change in permeability determine the transition between efflorescence and salt precipitation in the bulk. This research was supported by the Air Force Office of Scientific Research (AFOSR) under Award FA9550-09-1-0669-DOD35CAP and the Kavli Institute for Bionano Science and Technology at Harvard University.

  4. Finite volume hydromechanical simulation in porous media

    Science.gov (United States)

    Nordbotten, Jan Martin

    2014-05-01

    Cell-centered finite volume methods are prevailing in numerical simulation of flow in porous media. However, due to the lack of cell-centered finite volume methods for mechanics, coupled flow and deformation is usually treated either by coupled finite-volume-finite element discretizations, or within a finite element setting. The former approach is unfavorable as it introduces two separate grid structures, while the latter approach loses the advantages of finite volume methods for the flow equation. Recently, we proposed a cell-centered finite volume method for elasticity. Herein, we explore the applicability of this novel method to provide a compatible finite volume discretization for coupled hydromechanic flows in porous media. We detail in particular the issue of coupling terms, and show how this is naturally handled. Furthermore, we observe how the cell-centered finite volume framework naturally allows for modeling fractured and fracturing porous media through internal boundary conditions. We support the discussion with a set of numerical examples: the convergence properties of the coupled scheme are first investigated; second, we illustrate the practical applicability of the method both for fractured and heterogeneous media.

  5. Magnetite nanoparticles embedded in biodegradable porous silicon

    Energy Technology Data Exchange (ETDEWEB)

    Granitzer, P., E-mail: petra.granitzer@uni-graz.a [Institute of Physics, Karl Franzens University Graz, Universitaetsplatz 5, 8010 Graz (Austria); Institute for Electron Microscopy, University of Technology Graz, Steyrergasse 17, 8010 Graz (Austria); Rumpf, K. [Institute of Physics, Karl Franzens University Graz, Universitaetsplatz 5, 8010 Graz (Austria); Roca, A.G.; Morales, M.P. [Instituto de Ciencia de Materiales de Madrid, CSIC, Sor Juana Ines de la Cruz 3, Cantoblanco, 28049 Madrid (Spain); Poelt, P.; Albu, M. [Institute for Electron Microscopy, University of Technology Graz, Steyrergasse 17, 8010 Graz (Austria)

    2010-05-15

    Magnetite nanoparticles, which are coated with oleic acid in a hexane solution and exhibit an average diameter of 7.7 nm, were embedded in a porous silicon (PS) matrix by immersion under defined parameters (e.g. concentration, temperature, time). The porous silicon matrix is prepared by anodization of a highly n-doped silicon wafer in an aqueous HF-solution. Magnetic characterization of the samples has been performed by SQUID-magnetometry. The superparamagnetic behaviour of the magnetite nanoparticles is represented by temperature-dependent magnetization measurements. Zero field (ZFC)/field cooled (FC) experiments indicate magnetic interactions between the particles. For the infiltration into the PS-templates different concentrations of the magnetite nanoparticles are used and magnetization measurements are performed in respect with magnetic interactions between the particles. The achieved porous silicon/magnetite specimens are not only interesting due to their transition between superparamagnetic and ferromagnetic behaviour, and thus for magnetic applications but also because of the non-toxicity of both materials giving the opportunity to employ the system in medical applications as drug delivery or in medical diagnostics.

  6. Electrochemical Method of Making Porous Particles Using a Constant Current Density

    Science.gov (United States)

    Ferrari, Mauro (Inventor); Liu, Xuewu (Inventor); Cheng, Ming-Cheng (Inventor)

    2014-01-01

    Provided is a particle that includes a first porous region and a second porous region that differs from the first porous region. Also provided is a particle that has a wet etched porous region and that does have a nucleation layer associated with wet etching. Methods of making porous particles are also provided.

  7. Lifting a large object from an anisotropic porous bed

    Science.gov (United States)

    Karmakar, Timir; Raja Sekhar, G. P.

    2016-09-01

    An analytical study of two dimensional problem of lifting an object from the top of a fully saturated rigid porous bed is discussed. It is assumed that the porous bed is anisotropic in nature. The flow within the gap region between the object and the porous bed is assumed to be governed by Stokes equation while the flow within the porous bed is governed by Brinkman equation. The breakout phenomenon for different kinds of soil is reported. The effect of mechanical properties like anisotropic permeability, grain diameter size, and porosity on streamlines, velocity, and force is analyzed. Relevant comparison with C. C. Mei, R. W. Yeung, and K. F. Liu ["Lifting a large object from a porous bed," J. Fluid. Mech. 152, 203-215 (1985)] and Y. Chang, L. H. Huang and F. P. Y. Yang ["Two-dimensional lift-up problem for a rigid porous bed," Phys. Fluids, 27, 053101 (2015)] is done.

  8. Porosity-dependent fractal nature of the porous silicon surface

    Energy Technology Data Exchange (ETDEWEB)

    Rahmani, N.; Dariani, R. S., E-mail: dariani@alzahra.ac.ir [Department of Physics, Alzahra University, Tehran, 1993893973 (Iran, Islamic Republic of)

    2015-07-15

    Porous silicon films with porosity ranging from 42% to 77% were fabricated by electrochemical anodization under different current density. We used atomic force microscopy and dynamic scaling theory for deriving the surface roughness profile and processing the topography of the porous silicon layers, respectively. We first compared the topography of bare silicon surface with porous silicon and then studied the effect of the porosity of porous silicon films on their scaling behavior by using their self-affinity nature. Our work demonstrated that silicon compared to the porous silicon films has the highest Hurst parameter, indicating that the formation of porous layer due to the anodization etching of silicon surface leads to an increase of its roughness. Fractal analysis revealed that the evolution of the nanocrystallites’ fractal dimension along with porosity. Also, we found that both interface width and Hurst parameter are affected by the increase of porosity.

  9. SPUTTERING FROM A POROUS MATERIAL BY PENETRATING IONS

    Energy Technology Data Exchange (ETDEWEB)

    Rodriguez-Nieva, J. F. [Instituto Balseiro, Universidad Nacional de Cuyo, 8400 Bariloche (Argentina); Bringa, E. M. [CONICET and Instituto de Ciencias Basicas, Universidad Nacional de Cuyo, 5500 Mendoza (Argentina); Cassidy, T. A. [CalTech/JPL, Pasadena, CA 91109 (United States); Johnson, R. E.; Fama, M.; Baragiola, R. A. [Laboratory for Atomic and Surface Physics, University of Virginia, Charlottesville, VA 22903 (United States); Caro, A. [Los Alamos National Laboratory, Los Alamos, NM 94551 (United States); Loeffler, M. J. [NASA Goddard Space Flight Center, Astrochemistry Branch, Code 691, Greenbelt, MD 20771 (United States); Farkas, D. [Department of Materials Sciences, Virginia Tech, Blacksburg, VA 24061 (United States)

    2011-12-10

    Porous materials are ubiquitous in the universe and weathering of porous surfaces plays an important role in the evolution of planetary and interstellar materials. Sputtering of porous solids in particular can influence atmosphere formation, surface reflectivity, and the production of the ambient gas around materials in space. Several previous studies and models have shown a large reduction in the sputtering of a porous solid compared to the sputtering of the non-porous solid. Using molecular dynamics simulations we study the sputtering of a nanoporous solid with 55% of the solid density. We calculate the electronic sputtering induced by a fast, penetrating ion, using a thermal spike representation of the deposited energy. We find that sputtering for this porous solid is, surprisingly, the same as that for a full-density solid, even though the sticking coefficient is high.

  10. Sputtering from a Porous Material by Penetrating Ions

    Science.gov (United States)

    Rodriguez-Nieva, J. F.; Bringa, E. M.; Cassidy, T. A.; Johnson, R. E.; Caro, A.; Fama, M.; Loeffler, M. J.; Baragiola, R. A.; Farkas, D.

    2011-12-01

    Porous materials are ubiquitous in the universe and weathering of porous surfaces plays an important role in the evolution of planetary and interstellar materials. Sputtering of porous solids in particular can influence atmosphere formation, surface reflectivity, and the production of the ambient gas around materials in space. Several previous studies and models have shown a large reduction in the sputtering of a porous solid compared to the sputtering of the non-porous solid. Using molecular dynamics simulations we study the sputtering of a nanoporous solid with 55% of the solid density. We calculate the electronic sputtering induced by a fast, penetrating ion, using a thermal spike representation of the deposited energy. We find that sputtering for this porous solid is, surprisingly, the same as that for a full-density solid, even though the sticking coefficient is high.

  11. Review on Fractal Analysis of Porous Metal Materials

    Directory of Open Access Journals (Sweden)

    J. Z. Wang

    2015-01-01

    Full Text Available Porous metal materials are multifunctional lightweight materials and have been used widely in industry. The structural and functional characters of porous metal materials depend on the pore structure which can be described effectively by the fractal theory. This paper reviews the major achievements on fractal analysis of pore structure of porous metal materials made by State Key Laboratory of Porous Metal Materials, China, over the past few years. These include (i designing and developing a set of novel fractal analytical software of porous metal materials, (ii the influence of material characterization and image processing method on the fractal dimension, and (iii the relationship between the material performance and the fractal dimension. Finally, the outlooks of fractal theory applied in porous metal materials are discussed.

  12. OPM: The Open Porous Media Initiative

    Science.gov (United States)

    Flemisch, B.; Flornes, K. M.; Lie, K.; Rasmussen, A.

    2011-12-01

    The principal objective of the Open Porous Media (OPM) initiative is to develop a simulation suite that is capable of modeling industrially and scientifically relevant flow and transport processes in porous media and bridge the gap between the different application areas of porous media modeling, including reservoir mechanics, CO2 sequestration, biological systems, and product development of engineered media. The OPM initiative will provide a long-lasting, efficient, and well-maintained open-source software for flow and transport in porous media built on modern software principles. The suite is released under the GNU General Public License (GPL). Our motivation is to provide a means to unite industry and public research on simulation of flow and transport in porous media. For academic users, we seek to provide a software infrastructure that facilitates testing of new ideas on models with industry-standard complexity, while at the same time giving the researcher control over discretization and solvers. Similarly, we aim to accelerate the technology transfer from academic institutions to professional companies by making new research results available as free software of professional standard. The OPM initiative is currently supported by six research groups in Norway and Germany and funded by existing grants from public research agencies as well as from Statoil Petroleum and Total E&P Norge. However, a full-scale development of the OPM initiative requires substantially more funding and involvement of more research groups and potential end users. In this talk, we will provide an overview of the current activities in the OPM initiative. Special emphasis will be given to the demonstration of the synergies achieved by combining the strengths of individual open-source software components. In particular, a new fully implicit solver developed within the DUNE-based simulator DuMux could be enhanced by the ability to read industry-standard Eclipse input files and to run on

  13. Nano/macro porous bioactive glass scaffold

    Science.gov (United States)

    Wang, Shaojie

    Bioactive glass (BG) and ceramics have been widely studied and developed as implants to replace hard tissues of the musculo-skeletal system, such as bones and teeth. Recently, instead of using bulk materials, which usually do not degrade rapidly enough and may remain in the human body for a long time, the idea of bioscaffold for tissue regeneration has generated much interest. An ideal bioscaffold is a porous material that would not only provide a three-dimensional structure for the regeneration of natural tissue, but also degrade gradually and, eventually be replaced by the natural tissue completely. Among various material choices the nano-macro dual porous BG appears as the most promising candidate for bioscaffold applications. Here macropores facilitate tissue growth while nanopores control degradation and enhance cell response. The surface area, which controls the degradation of scaffold can also be tuned by changing the nanopore size. However, fabrication of such 3D structure with desirable nano and macro pores has remained challenging. In this dissertation, sol-gel process combined with spinodal decomposition or polymer sponge replication method has been developed to fabricate the nano-macro porous BG scaffolds. Macropores up to 100microm are created by freezing polymer induced spinodal structure through sol-gel transition, while larger macropores (>200um) of predetermined size are obtained by the polymer sponge replication technique. The size of nanopores, which are inherent to the sol-gel method of glass fabrication, has been tailored using several approaches: Before gel point, small nanopores are generated using acid catalyst that leads to weakly-branched polymer-like network. On the other hand, larger nanopores are created with the base-catalyzed gel with highly-branched cluster-like structure. After the gel point, the nanostructure can be further modified by manipulating the sintering temperature and/or the ammonia concentration used in the solvent

  14. Modeling approaches to natural convection in porous media

    CERN Document Server

    Su, Yan

    2015-01-01

    This book provides an overview of the field of flow and heat transfer in porous medium and focuses on presentation of a generalized approach to predict drag and convective heat transfer within porous medium of arbitrary microscopic geometry, including reticulated foams and packed beds. Practical numerical methods to solve natural convection problems in porous media will be presented with illustrative applications for filtrations, thermal storage and solar receivers.

  15. Investigation on porous frequency of regenerator of microminiature thermoacoustic refrigerator

    Institute of Scientific and Technical Information of China (English)

    LIU Yi-cai; ZHOU Jie-min; ZHOU Nai-jun; LIAO Sheng-ming

    2005-01-01

    A new method was proposed to directly measure the effective resistance and distinguish the porous frequency in the regenerator of the microminiature thermoacoustic refrigerator. Measured results were compared with the flux gain factor and transmission loss of the real system. The results show that the agreement between the range of the porous frequency and frequency of the system is good, the method can be used to predict the porous frequency of the regenerator in production.

  16. Review of enhanced vapor diffusion in porous media

    International Nuclear Information System (INIS)

    Vapor diffusion in porous media in the presence of its own liquid has often been treated similar to gas diffusion. The gas diffusion rate in porous media is much lower than in free space due to the presence of the porous medium and any liquid present. However, enhanced vapor diffusion has also been postulated such that the diffusion rate may approach free-space values. Existing data and models for enhanced vapor diffusion, including those in TOUGH2, are reviewed in this paper

  17. Porous and Complex Flow Structures in Modern Technologies

    OpenAIRE

    Bejan, A.; Dincer, I.; S. Lorente; Miguel, A. F.; A. H. Reis

    2004-01-01

    Porous and Complex Flow Structures in Modern Technologies represents a new approach to the field, considering the fundamentals of porous media in terms of the key roles played by these materials in modern technology. Intended as a text for advanced undergraduates and as a reference for practicing engineers, the book uses the physics of flows in porous materials to tie together a wide variety of important issues from such fields as biomedical engineering, energy conversion, civil engineering, ...

  18. Porous Flame-retarded Asphalt Pavement for Highway Tunnel

    Institute of Scientific and Technical Information of China (English)

    HU Shuguang; HUANG Shaolong; Ding Qingjun

    2008-01-01

    A new way to improve the tunnel fire protection by using flame-retarded porous asphalt pavement containing ATH powders was introduced. Based on the miniature burning test designed and conducted, the burning time and temperature of porous asphalt (PA) and flame-retarded porous asphalt (FRPA) were studied comparing with cement concrete pavement, dense-graded HMA and S MA. Results of burning test and pavement performance test indicate that FRPA is appropriate and suitable as the pavement material of highway tunnel.

  19. Fractal Character for Tortuous Streamtubes in Porous Media

    Institute of Scientific and Technical Information of China (English)

    YU Bo-Ming

    2005-01-01

    @@ An analytical modelfor fractal dimension of tortuous streamtubes in porous media is derived. The proposed fractal dimension for tortuous streamtubes in porous media is expressed as a function of porosity and scale, and there is no empirical constant in the proposed expression. The model predictions for the fractal dimension oftortuous streamtubes in porous media are in good agreement with those by the box-counting method and with the observations of other researchers.

  20. Aerodynamic and acoustic integral characteristics of porous rotors

    OpenAIRE

    Benedik, Gašper; Eberlinc, Matjaž; Hočevar, Marko; Širok, Brane

    2015-01-01

    This paper describes porous rotors manufactured from open cell aluminium foam. Rotor construction and theoretical description of fluid flow through rotating porous material are presented. Nine porous rotors made of materials with three different average pore sizes, with or without inducer, three rotor heights and two inlet diameters were selected and compared to a classical rotor with blades. Measurements involved two parts, measurement of pressure drop on non-rotating rotors while integral f...

  1. Numerical Simulation of thePorous Structure of Biomaterials

    Institute of Scientific and Technical Information of China (English)

    WANGHui-min; YANYu-hua; LIShi-pu

    2004-01-01

    Porous biomaterials are widely used as bone replacement materials because of thers high biocompatibility and osteoconductivity property. Understanding of their porous structure (i. e. geometrical and topological characteristic) and studying how to the body fluid flow through them are essential to investigate thed egradation behaviour at the surface-liquid interface. This research develops a numerical model to simulate the porous structure of biomaterials based on the stochastic approach in pore size distribution and interconnectivity.

  2. Solvent-mediated secondary building units (SBUs) diversification in a series of MnII-based metal-organic frameworks (MOFs)

    Science.gov (United States)

    Niu, Yan-Fei; Cui, Li-Ting; Han, Jie; Zhao, Xiao-Li

    2016-09-01

    The role of auxiliary solvents in the formation of MOFs has been investigated for a series of MnII-based framework systems. Reactions of 4,4‧,4″-nitrilotribenzoic acid (H3L) with MnII through varying auxiliary solvents of the medium resulted in the formation of diversified multinuclear MnII subunits in four new coordination polymers: [Mn3(L)(HCOO)3(DEF)3] (1), [Mn3(L)2(EtOH)2]·DMF (2), [Mn5(L)4(H2O)2]·2(H2NMe2)+·4DMF·2H2O (3), and [Mn3(L)2(py)4(H2O)]·H2O (4) (H3L=4,4‧,4‧-nitrilotribenzoic acid, DMF=dimethylformamide, DEF=N,N-diethylformamide, py=pyridine). These four compounds were fully characterized by single-crystal X-ray diffraction, showing interesting SBUs variations. For compound 1, it displays a (3,6)-connected kgd net with wheel [Mn6] cluster serving as SBU, whereas in 2, the sequence of Mn3(COO)9(EtOH)2 is repeated by inversion centers located between Mn1 and Mn3 to form an infinite Mn-carboxylate chain, which are further interlinked by L3- ligands to form a 3D architecture. In 3, the pentanuclear Mn5(CO2)12 clusters are interlinked to form a layer, which are further pillared by L3- to generate a 3D network. Compound 4 has a (3,6)-connected network in which the SBU is a linear trimeric Mn3(COO)6(py)4(H2O) cluster. In addition, the thermal stabilities, X-ray powder diffraction of all the compounds were studied, photoluminescence behaviors of compounds 1, 3 and 4 are discussed.

  3. Passive cooling of porous tile used on external wall

    Institute of Scientific and Technical Information of China (English)

    罗庆; 刘庆开; 夏煦

    2009-01-01

    The porous tiles under the dry and wet conditions were studied. The simplified mathematical model was put forward to simulate the procedure of moisture evaporating for the densely porous tile. The results show that the capability of passive cooling of the porous tile is more than 5 ℃ with moisture content of 30% in Yangtze river region. Through the comparison between the measuring and simulating data,it can be proved that the simplified math model can be fully used to the engineering application,which provides a reference to explore the thermal performance of other porous material.

  4. Characteristics of porous zirconia coated with hydroxyapatite as human bones

    Indian Academy of Sciences (India)

    V V Narulkar; S Prakash; K Chandra

    2007-08-01

    Since hydroxyapatite has excellent biocompatibility and bone bonding ability, porous hydroxyapatite ceramics have been intensively studied. However, porous hydroxyapatite bodies are mechanically weak and brittle, which makes shaping and implantation difficult. One way to solve this problem is to introduce a strong porous network onto which hydroxyapatite coating is applied. In this study, porous zirconia and alumina-added zirconia ceramics were prepared by ceramic slurry infiltration of expanded polystyrene bead compacts, followed by firing at 1500°C. Then slurry of hydroxyapatite–borosilicate glass mixed powder was used to coat the porous ceramics, followed by firing at 1200°C. The porous structures without the coating had high porosities of 51–69%, high pore interconnectivity, and sufficiently large pore window sizes (300–500 m). The porous ceramics had compressive strengths of 5.3∼36.8 MPa, favourably comparable to the mechanical properties of cancellous bones. In addition, porous hydroxyapatite surface was formed on the top of the composite coating, whereas a borosilicate glass layer was found on the interface. Thus, porous zirconia-based ceramics were modified with a bioactive composite coating for biomedical applications.

  5. Porous waveguide facilitated low divergence quantum cascade laser*

    Institute of Scientific and Technical Information of China (English)

    Yin Wen; Lu Quanyong; Liu Wannfeng; Zhang Jinchuan; Wang Lijun; Liu Junqi; Li Lu; Liu Fengqi; Wang Zhanguo

    2011-01-01

    A quantum cscade laser with a porous waveguide structure emitting at 4.5 μm is reported. A branchlike porous structure filled with metal material was fabricated on both sides of the laser ridge by an electrochemical etching process. In contrast to the common ridge waveguide laser, devices with a porous structure give rather better beam quality. Utilizing this porous structure as a high-order mode absorber, the device exhibited fundamental transverse mode emission with a nearly diffraction limited far-field beam divergence angle of 4.9°.

  6. Comparison of the mass transfer in totally porous and superficially porous stationary phases in liquid chromatography.

    Science.gov (United States)

    Kiss, Ibolya; Bacskay, Ivett; Kilár, Ferenc; Felinger, Attila

    2010-06-01

    The characterization of mass-transfer processes in a chromatographic column during a separation process is essential, since the influence of the mass-transfer kinetics on the shape of the chromatographic band profiles and on the efficiency of the separation is crucial. Several sources of mass transfer in a chromatographic bed have been identified and studied: the axial dispersion in the stream of mobile phase, the external mass-transfer resistance, intraparticle diffusion, and the kinetics of adsorption-desorption. We measured and compared the characteristics and performance of a new brand of shell particles and those of a conventional brand of totally porous silica particles. The shell stationary phase was made of 2.7-microm superficially porous particles (a 1.7-microm solid core is covered with a 0.5-microm-thick shell of porous silica). The other material consisted of totally porous particles of conventional 3.5-microm commercial silica. We measured the first and second central moments of the peaks of human insulin over a wide range of mobile phase velocities (from 0.02 to 1.3 mL/min) at 20 degrees C. The plate height equations were constructed and the axial dispersion, external mass transfer, as well as the intraparticle diffusion coefficients were calculated for the two stationary phases.

  7. REVIEW ON POROUS AND NON-POROUS FLAT PLATE AIR COLLECTOR WITH MIRROR ENCLOSURE

    Directory of Open Access Journals (Sweden)

    M. PRADHAPRAJ,

    2010-09-01

    Full Text Available In solar air heater, flat plat collectors are the best heat transferring devices. But the effectiveness of these collectorsis very low because of lack of technology. Solar assisted heated air is successfully used for drying applications and space heating under controlled conditions. From the solar flat plate air heater the hot air is transferred to a conventional dryer or to the combined heater and drying chamber directly. Hence, solar assisted air heaters arecheaper and reliable. The important factors affecting these systems are the solar radiation, mechanical loading, temperature and leakage. The air heater efficiency depends on the design of the system as well as the construction materials and the assembly. The solar air heating systems has acceptable life span of 15 to 20 years. The addition ofside mirror enclosures is to increase the amount of solar radiation absorption at the collector plate so that the collector increases the yield and operate in a higher temperature range. Therefore with the addition of side mirrors one can able to maximize the output of fixed flat plate collectors. A flat plate air collector will be more efficient if it is made up of porous medium when comparing it with the non porous collectors according to the study. In this paper, the performances of porous and non-porous absorber plates are discussed. Also the possible methods of finding out air leakages and the methodology adopted for the performance and efficiency calculations are also discussed.

  8. The biocompatibility of porous vs non-porous bone cements: a new methodological approach

    Directory of Open Access Journals (Sweden)

    C. Dall'Oca

    2014-06-01

    Full Text Available Composite cements have been shown to be biocompatible, bioactive, with good mechanical properties and capability to bind to the bone. Despite these interesting characteristic, in vivo studies on animal models are still incomplete and ultrastructural data are lacking. The acquisition of new ultrastructural data is hampered by uncertainties in the methods of preparation of histological samples due to the use of resins that melt methacrylate present in bone cement composition. A new porous acrylic cement composed of polymethylmetacrylate (PMMA and β-tricalciumphosphate (β-TCP was developed and tested on an animal model. The cement was implanted in femurs of 8 New Zealand White rabbits, which were observed for 8 weeks before their sacrifice. Histological samples were prepared with an infiltration process of LR white resin and then the specimens were studied by X-rays, histology and scanning electron microscopy (SEM. As a control, an acrylic standard cement, commonly used in clinical procedures, was chosen. Radiographic ultrastructural and histological exams have allowed finding an excellent biocompatibility of the new porous cement. The high degree of osteointegration was demonstrated by growth of neo-created bone tissue inside the cement sample. Local or systemic toxicity signs were not detected. The present work shows that the proposed procedure for the evaluation of biocompatibility, based on the use of LR white resin allows to make a thorough and objective assessment of the biocompatibility of porous and non-porous bone cements.

  9. Fatigue behavior of porous biomaterials manufactured using selective laser melting.

    Science.gov (United States)

    Yavari, S Amin; Wauthle, R; van der Stok, J; Riemslag, A C; Janssen, M; Mulier, M; Kruth, J P; Schrooten, J; Weinans, H; Zadpoor, A A

    2013-12-01

    Porous titanium alloys are considered promising bone-mimicking biomaterials. Additive manufacturing techniques such as selective laser melting allow for manufacturing of porous titanium structures with a precise design of micro-architecture. The mechanical properties of selective laser melted porous titanium alloys with different designs of micro-architecture have been already studied and are shown to be in the range of mechanical properties of bone. However, the fatigue behavior of this biomaterial is not yet well understood. We studied the fatigue behavior of porous structures made of Ti6Al4V ELI powder using selective laser melting. Four different porous structures were manufactured with porosities between 68 and 84% and the fatigue S-N curves of these four porous structures were determined. The three-stage mechanism of fatigue failure of these porous structures is described and studied in detail. It was found that the absolute S-N curves of these four porous structures are very different. In general, given the same absolute stress level, the fatigue life is much shorter for more porous structures. However, the normalized fatigue S-N curves of these four structures were found to be very similar. A power law was fitted to all data points of the normalized S-N curves. It is shown that the measured data points conform to the fitted power law very well, R(2)=0.94. This power law may therefore help in estimating the fatigue life of porous structures for which no fatigue test data is available. It is also observed that the normalized endurance limit of all tested porous structures (<0.2) is lower than that of corresponding solid material (c.a. 0.4).

  10. Characterizing unsaturated diffusion in porous tuff gravel

    International Nuclear Information System (INIS)

    Evaluation of solute diffusion in unsaturated porous gravel is very important for investigations of contaminant transport and remediation, risk assessment, and waste disposal (for example, the potential high-level nuclear waste repository at Yucca Mountain, Nevada). For a porous aggregate medium such as granular tuff, the total water content is comprised of surface water and interior water. The surface water component (water film around grains and pendular water between the grain contacts) could serve as a predominant diffusion pathway. To investigate the extent to which surface water films and contact points affect solute diffusion in unsaturated gravel, we examined the configuration of water using x-ray computed tomography in partially saturated gravel, and made quantitative measurements of diffusion at multiple water contents using two different techniques. In the first, diffusion coefficients of potassium chloride in 2-4 mm granular tuff at multiple water contents were calculated from electrical conductivity measurements using the Nernst-Einstein equation. In the second, we used laser ablation with inductively coupled plasma-mass spectrometry to perform micro-scale mapping, allowing the measurement of diffusion coefficients for a mixture of chemical tracers for tuff cubes and tetrahedrons having two contact geometries (cube-cube and cube-tetrahedron). The x-ray computed tomography images show limited contact between grains, and this could hinder the pathways for diffusive transport. Experimental results show the critical role of surface water in controlling transport pathways and hence the magnitude of diffusion. Even with a bulk volumetric water content of 1.5%, the measured solute diffusion coefficient is as low as 1.5 x 10-14 m2/s for tuff gravel. Currently used diffusion models relating diffusion coefficients to total volumetric water content inadequately describe unsaturated diffusion behavior in porous gravel at very low water contents

  11. Hydrocarbons biodegradation in unsaturated porous medium

    International Nuclear Information System (INIS)

    Biological processes are expected to play an important role in the degradation of petroleum hydrocarbons in contaminated soils. However, factors influencing the kinetics of biodegradation are still not well known, especially in the unsaturated zone. To address these biodegradation questions in the unsaturated zone an innovative experimental set up based on a physical column model was developed. This experimental set up appeared to be an excellent tool for elaboration of a structured porous medium, with well defined porous network and adjusted water/oil saturations. Homogeneous repartition of both liquid phases (i.e., aqueous and non aqueous) in the soil pores, which also contain air, was achieved using ceramic membranes placed at the bottom of the soil column. Reproducible interfaces (and connectivity) are developed between gas, and both non mobile water and NAPL phases, depending on the above-defined characteristics of the porous media and on the partial saturations of these three phases (NAPL, water and gas). A respirometric apparatus was coupled to the column. Such experimental set up have been validated with hexadecane in dilution in an HMN phase. This approach allowed detailed information concerning n-hexadecane biodegradation, in aerobic condition, through the profile of the oxygen consumption rate. We have taken benefit of this technique, varying experimental conditions, to determine the main parameters influencing the biodegradation kinetics and compositional evolution of hydrocarbons, under steady state unsaturated conditions and with respect to aerobic metabolism. Impacts of the nitrogen quantity and of three different grain sizes have been examined. Biodegradation of petroleum cut, as diesel cut and middle distillate without aromatic fraction, were, also studied. (author)

  12. Porous-shaped silicon carbide ultraviolet photodetectors on porous silicon substrates

    Energy Technology Data Exchange (ETDEWEB)

    Naderi, N., E-mail: naderi.phd@gmail.com [Nano-Optoelectronics Research Laboratory, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang (Malaysia); Hashim, M.R. [Nano-Optoelectronics Research Laboratory, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang (Malaysia)

    2013-03-05

    Highlights: ► Porous-shaped silicon carbide thin film was deposited on porous silicon substrate. ► Thermal annealing was followed to enhance the physical properties of samples. ► Metal–semiconductor-metal ultraviolet detectors were fabricated on samples. ► The effect of annealing temperature on electrical performance of devices was studied. ► The efficiency of photodetectors was enhanced by annealing at elevated temperatures. -- Abstract: A metal–semiconductor-metal (MSM) ultraviolet photodetector was fabricated based on a porous-shaped structure of silicon carbide (SiC). For increasing the surface roughness of SiC and hence enhancing the light absorption effect in fabricated devices, porous silicon (PS) was chosen as a template; SiC was deposited on PS substrates via radio frequency magnetron sputtering. Therefore, the deposited layers followed the structural pattern of PS skeleton and formed a porous-shaped SiC layer on PS substrate. The structural properties of samples showed that the as-deposited SiC was amorphous. Thus, a post-deposition annealing process with elevated temperatures was required to convert its amorphous phase to crystalline phase. The morphology of the sputtered samples was examined via scanning electron and atomic force microscopies. The grain size and roughness of the deposited layers clearly increased upon an increase in the annealing temperature. The optical properties of sputtered SiC were enhanced due to applying high temperatures. The most intense photoluminescence peak was observed for the sample with 1200 °C of annealing temperature. For the metallization of the SiC substrates to fabricate MSM photodetectors, two interdigitated Schottky contacts of Ni with four fingers for each electrode were deposited onto all the porous substrates. The optoelectronic characteristics of MSM UV photodetectors with porous-shaped SiC substrates were studied in the dark and under UV illumination. The electrical characteristics of fabricated

  13. Diffusion of oriented particles in porous media

    Energy Technology Data Exchange (ETDEWEB)

    Haber, René [Institut für Physik, Technische Universität Chemnitz, D-09107 Chemnitz (Germany); Centre for Nonlinear Studies, Institute of Cybernetics at Tallinn University of Technology, Akadeemia tee 21, 12618 Tallinn (Estonia); Prehl, Janett [Institut für Physik, Technische Universität Chemnitz, D-09107 Chemnitz (Germany); Herrmann, Heiko [Centre for Nonlinear Studies, Institute of Cybernetics at Tallinn University of Technology, Akadeemia tee 21, 12618 Tallinn (Estonia); Hoffmann, Karl Heinz, E-mail: hoffmann@physik.tu-chemnitz.de [Institut für Physik, Technische Universität Chemnitz, D-09107 Chemnitz (Germany)

    2013-11-29

    Diffusion of particles in porous media often shows subdiffusive behavior. Here, we analyze the dynamics of particles exhibiting an orientation. The features we focus on are geometrical restrictions and the dynamical consequences of the interactions between the local surrounding structure and the particle orientation. This interaction can lead to particles getting temporarily stuck in parts of the structure. Modeling this interaction by a particular random walk dynamics on fractal structures we find that the random walk dimension is not affected while the diffusion constant shows a variety of interesting and surprising features.

  14. Template-directed porous electrodes in electroanalysis.

    Science.gov (United States)

    Walcarius, Alain

    2010-01-01

    Nano- and/or macrostructuring of electrode surfaces has recently emerged as a powerful method of improving the performances of electrochemical devices by enhancing both molecular accessibility and rapid mass transport via diffusion, by increasing the electroactive surface area in comparison to the geometric one, and/or by providing confinement platforms for hosting suitable reagents. This brief overview highlights how template technology offers advantages in terms of designing new types of porous electrodes-mostly based on thin films, and functionalized or not-and discusses their use in analytical chemistry via some recent examples from the literature on electrochemical sensors and biosensors.

  15. Nanotube Arrays in Porous Anodic Alumina Membranes

    Institute of Scientific and Technical Information of China (English)

    Liang LI; Naoto KOSHIZAKI; Guanghai LI

    2008-01-01

    This review summarizes the various techniques developed for fabricating nanotube arrays in porous anodic alumina membranes (AAMs). After a brief introduction to the fabrication process of AAMs, taking carbons, metals, semiconductors, organics, biomoleculars, and heterojunctions as typical examples, attention will be focused on the recently established methods to fabricate nanotubes in AAM, including electrochemical deposition, surface sol-gel, modified chemical vapor deposition, atomic layer deposition, and layer-by-layer growth. Every method is demonstrated by one or two reported results. Finally, this review is concluded with some perspectives on the research directions and focuses on the AAM-based nanotubes fields.

  16. Robust and Porous β-Diketiminate-Functionalized Metal–Organic Frameworks for Earth-Abundant-Metal-Catalyzed C–H Amination and Hydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    Thacker, Nathan C.; Lin, Zekai; Zhang, Teng; Gilhula, James C.; Abney, Carter W.; Lin, Wenbin (UC)

    2016-05-27

    We have designed a strategy for postsynthesis installation of the β-diketiminate (NacNac) functionality in a metal–organic framework (MOF) of UiO-topology. Metalation of the NacNac-MOF (I) with earth-abundant metal salts afforded the desired MOF-supported NacNac-M complexes (M = Fe, Cu, and Co) with coordination environments established by detailed EXAFS studies. The NacNac-Fe-MOF catalyst, I•Fe(Me), efficiently catalyzed the challenging intramolecular sp3 C–H amination of a series of alkyl azides to afford α-substituted pyrrolidines. The NacNac-Cu-MOF catalyst, I•Cu(THF), was effective in promoting the intermolecular sp3 C–H amination of cyclohexene using unprotected anilines to provide access to secondary amines in excellent selectivity. Finally, the NacNac-Co-MOF catalyst, I•Co(H), was used to catalyze alkene hydrogenation with turnover numbers (TONs) as high as 700 000. All of the NacNac-M-MOF catalysts were more effective than their analogous homogeneous catalysts and could be recycled and reused without a noticeable decrease in yield. The NacNac-MOFs thus provide a novel platform for engineering recyclable earth-abundant-element-based single-site solid catalysts for many important organic transformations.

  17. Environmental corrosion resistance of porous TiAl intermetallic compounds

    Institute of Scientific and Technical Information of China (English)

    ZHENG Zhi; JIANG Yao; DONG Hong-xing; TANG Lie-min; HE Yue-hui; HUANG Bai-yun

    2009-01-01

    Porous TiAl intermetallic compound, as a novel substitute for current inorganic porous material, offsets the shortages of both ceramics and metals. The environmental corrosion resistance of porous TiAl intermetallic compound was investigated. The kinetic equation for the cyclic oxidation of porous TiAl alloy at 600 ℃ is determined to be Δm2=1.08×10-5t. After total oxidation of 140 h, porous TiAl intermetallic compound shows more stability of pore structure and the mass gain of TiAl alloy is 0.042 g/m2, which is only 10.6% that of porous 316L stainless steel. The kinetic equation for the cyclic corrosion behavior of porous TiAl alloy in hydrochloric acid with pH=2 at 90 ℃ is determined to be Δm2=5.41×10-5t-2.08×10-4. After 50 h exposure, the mass loss of TiAl alloy is 0.049 g/m2, which is only 14.8% and 5.57% that of porous Ti and stainless steel, respectively. The kinetic equation in hydrochloric acid with pH=3 is determined to be Δm2=2.63×10-6t-3.72×10-6.

  18. Deposited Micro Porous Layer as Lubricant Carrier in Metal Forming

    DEFF Research Database (Denmark)

    Arentoft, Mogens; Bay, Niels; Tang, Peter Torben;

    2008-01-01

    A new porous coating for carrying lubricant in metal forming processes is developed. The coating is established by simultaneous electrochemical deposition of two pure metals. One of them is subsequently etched away leaving a porous surface layer. Lubricant can be trapped in the pores acting as lu...

  19. Dynamic behavior of porous concretes under drop weight impact testing

    NARCIS (Netherlands)

    Agar Ozbek, A.S.; Weerheijm, J.; Schlangen, E.; Breugel, K. van

    2013-01-01

    Porous concrete is used as a construction material in various applications mainly as a permeable cementitious material. However, its response under impact loading is generally not considered. Due to the high percentage of its intentional meso-size air pores, porous concrete has a moderate static str

  20. Simulations on porous media with nanofluids-initial study

    Science.gov (United States)

    Zeidan, D.; Alnaief, M.; Saghir, M. Ziad; Touma, R.

    2016-06-01

    Numerical simulations of natural convection heat and mass transfer in a square cavity using Comsol Multiphysics 5.0 software are presented. The effective thermal conductivity of nanofluid in porous media is computed using glass beads as porous media. It is observed that the heat and mass transfer rate increases with the increase of temperature variation as well as nanoparticle volume concentration.

  1. Sulfur cathode hosted in porous organic polymeric matrices

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Zhengcheng; Weng, Wei; Yuan, Shengwen; Amine, Khalil

    2016-02-09

    A composite material includes a porous organic polymer and an electrochemically active material, wherein the porous organic polymer contains a plurality of pores having a diameter of from about 0.1 nm to about 100 nm, and the electrochemically active material is disposed within the pores.

  2. Experimental Evidence of Helical Flow in Porous Media

    DEFF Research Database (Denmark)

    Ye, Yu; Chiogna, Gabriele; Cirpka, Olaf A.;

    2015-01-01

    Helical flow leads to deformation of solute plumes and enhances transverse mixing in porous media. We present experiments in which macroscopic helical flow is created by arranging different materials to obtain an anisotropic macroscopic permeability tensor with spatially variable orientation. The...... mixers, but in porous media....

  3. Inorganic porous hollow fiber membranes : with tunable small radial dimensions

    NARCIS (Netherlands)

    Luiten-Olieman, M.W.J.

    2012-01-01

    The objectives of this thesis are twofold. The first aim is to develop of robust coating procedures for thin supported films onto porous ceramic supports. The second aim is the development of a preparation methodology for high quality porous inorganic membranes, with large membrane surface area. A r

  4. Visualizing Gas Adsorption on Porous Solids: Four Simple, Effective Demonstrations

    Science.gov (United States)

    Cheung, Ocean

    2014-01-01

    Gas adsorption on porous solids is a topic that is often discussed in an undergraduate chemistry or chemical engineering course. The idea of porosity and gas adsorption on a porous solid is usually discussed with adsorption isotherms recorded using commercially available equipment. This discussion can be rather abstract and can be difficult for…

  5. Electrocatalysts using porous polymers and method of preparation

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Di-Jia; Yuan, Shengwen; Goenaga, Gabriel A.

    2016-08-02

    A method of producing an electrocatalyst article using porous polymers. The method creates a porous polymer designed to receive transition metal groups disposed at ligation sites and activating the transition metals to form an electrocatalyst which can be used in a fuel cell. Electrocatalysts prepared by this method are also provided. A fuel cell which includes the electrocatalyst is also provided.

  6. The potentials of porous concrete for ballistic protection

    NARCIS (Netherlands)

    Weerheijm, J.; Roebroeks, G.; Krabbenborg, D.; Agar Ozbek, A.S.

    2015-01-01

    A special porous concrete has been developed by the Delft University in collaboration with TNO. The concrete has a static compressive strength of 45 MPa. It fragments at impact into small size debris relative to reference concrete. The porous concrete was developed at laboratory scale and tested at

  7. Porous silicon multitexture for photoelectric converter structures of solar energy

    Directory of Open Access Journals (Sweden)

    Yerokhov V. Yu.

    2009-06-01

    Full Text Available The possibility of creation of porous silicon’s multitexture, as material of structure of photoelectric converter (FEC is shown. The morphological elements of porous silicon are considered relative to different pore parameters. The integral coefficient of frontal surface reflection of FEC with using of columnar multitexture in the range from 400 nm up to 1150 nm decreased.

  8. Investigating porous concrete with improved strength: Testing at different scales

    NARCIS (Netherlands)

    Agar-Ozbek, A.S.; Weerheijm, J.; Schlangen, E.; Breugel, K. van

    2013-01-01

    Porous concrete incorporates a high percentage of meso-size air voids that makes its mechanical characteristics remarkably different from normal concrete. A research project was undertaken to design a special type of porous concrete, that fractures into small fragments when exposed to impact loading

  9. Synthesis of silica based porous nanomaterials

    Science.gov (United States)

    Mueller, Paul S.

    Silica is one of the most abundant elements on the planet, has flexible bonding properties and generally excellent stability. Because of these properties, silica has been a vital component in technologies ranging from ancient glassware to modern supercomputers. Silica is able to form a wide range of materials both alone and as a component of larger material frameworks. Porous silica based nanomaterials are rapidly growing in importance because of their many applications in a wide variety of fields. This thesis focuses on the synthesis of silica based porous nanomaterials: nanocrystalline zeolites, mesoporous silica nanoparticles, and iron oxide core/shell nanocomposites. The synthetic conditions of these materials were varied in order to maximize efficiency, minimize environmental impact, and produce high quality material with far reaching potential applications. The materials were characterized by physicochemical techniques including Transmission Electron Microscopy, Dynamic Light Scattering, Powder X-Ray Diffraction, Solid State NMR, and Nitrogen Adsorption Isotherms. The materials were evaluated and conditions were controlled to produce high yields of quality nanomaterials and hypothesize methods for further synthetic control. The products will be used in studies involving nanoparticle toxicity, environmental remediation, and drug delivery.

  10. Formation of porous α tantalum in films

    Science.gov (United States)

    Tuleushev, Yu. Zh.; Volodin, V. N.; Brodskii, A. R.

    2015-08-01

    Ta—Cd alloys in the form of coatings with up to 66.2 at % Cd are fabricated for the first time by ion-plasma sputtering and the subsequent codeposition of ultradispersed Ta and Cd particles. At a concentration higher than 44.0 at % Cd, tetragonal β-Ta transforms into bcc α-Ta. Beginning from 74.4 at %, cadmium forms its hexagonal lattice and tantalum in the coatings is represented by an amorphous phase. During vacuum heat treatment at 700-750°C, cadmium evaporates from the binary tantalum—cadmium system containing more than 74.4 at % Cd, and a porous tantalum coating with a well-developed surface forms. Tantalum in the coating is represented by various flakelike crystallites, and tantalum in the near-surface layer mainly has a globular shape. A comparison of the specific surface areas of a tantalum film and the porous tantalum coating, which is performed by the BET method, demonstrates that the specific surface area increases by 277.5 m2/g Ta. Our results can be applied to other binary systems having similar properties.

  11. Electrochemical impedance spectroscopy of oxidized porous silicon

    Energy Technology Data Exchange (ETDEWEB)

    Mula, Guido, E-mail: guido.mula@unica.it [Dipartimento di Fisica, Università degli Studi di Cagliari, Cittadella Universitaria di Monserrato, S.P. 8 km 0.700, 09042 Cagliari (Italy); Tiddia, Maria V. [Dipartimento di Fisica, Università degli Studi di Cagliari, Cittadella Universitaria di Monserrato, S.P. 8 km 0.700, 09042 Cagliari (Italy); Ruffilli, Roberta [Nanochemistry, Istituto Italiano di Tecnologia, Via Morego 30, 16163 Genova (Italy); Falqui, Andrea [Nanochemistry, Istituto Italiano di Tecnologia, Via Morego 30, 16163 Genova (Italy); Dipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari, Cittadella Universitaria di Monserrato, S.P. 8 km 0.700, 09042 Cagliari (Italy); Palmas, Simonetta; Mascia, Michele [Dipartimento di Ingegneria Meccanica Chimica e dei Materiali, Università degli Studi di Cagliari, Piazza d' Armi, 09126 Cagliari (Italy)

    2014-04-01

    We present a study of the electrochemical oxidation process of porous silicon. We analyze the effect of the layer thickness (1.25–22 μm) and of the applied current density (1.1–11.1 mA/cm{sup 2}, values calculated with reference to the external samples surface) on the oxidation process by comparing the galvanostatic electrochemical impedance spectroscopy (EIS) measurements and the optical specular reflectivity of the samples. The results of EIS were interpreted using an equivalent circuit to separate the contribution of different sample parts. A different behavior of the electrochemical oxidation process has been found for thin and thick samples: whereas for thin samples the oxidation process is univocally related to current density and thickness, for thicker samples this is no more true. Measurements by Energy Dispersive Spectroscopy using a Scanning Electron Microscopy confirmed that the inhomogeneity of the electrochemical oxidation process is increased by higher thicknesses and higher currents. A possible explanation is proposed to justify the different behavior of thin and thick samples during the electrochemical process. - Highlights: • A multidisciplinary approach on porous Si electrochemical oxidation is proposed. • Electrochemical, optical, and structural characterizations are used. • Layer thickness and oxidation current effects are shown. • An explanation of the observed behavior is proposed.

  12. Porous Titanium for Dental Implant Applications

    Directory of Open Access Journals (Sweden)

    Zena J. Wally

    2015-10-01

    Full Text Available Recently, an increasing amount of research has focused on the biological and mechanical behavior of highly porous structures of metallic biomaterials, as implant materials for dental implants. Particularly, pure titanium and its alloys are typically used due to their outstanding mechanical and biological properties. However, these materials have high stiffness (Young’s modulus in comparison to that of the host bone, which necessitates careful implant design to ensure appropriate distribution of stresses to the adjoining bone, to avoid stress-shielding or overloading, both of which lead to bone resorption. Additionally, many coating and roughening techniques are used to improve cell and bone-bonding to the implant surface. To date, several studies have revealed that porous geometry may be a promising alternative to bulk structures for dental implant applications. This review aims to summarize the evidence in the literature for the importance of porosity in the integration of dental implants with bone tissue and the different fabrication methods currently being investigated. In particular, additive manufacturing shows promise as a technique to control pore size and shape for optimum biological properties.

  13. Electrochemical impedance spectroscopy of oxidized porous silicon

    International Nuclear Information System (INIS)

    We present a study of the electrochemical oxidation process of porous silicon. We analyze the effect of the layer thickness (1.25–22 μm) and of the applied current density (1.1–11.1 mA/cm2, values calculated with reference to the external samples surface) on the oxidation process by comparing the galvanostatic electrochemical impedance spectroscopy (EIS) measurements and the optical specular reflectivity of the samples. The results of EIS were interpreted using an equivalent circuit to separate the contribution of different sample parts. A different behavior of the electrochemical oxidation process has been found for thin and thick samples: whereas for thin samples the oxidation process is univocally related to current density and thickness, for thicker samples this is no more true. Measurements by Energy Dispersive Spectroscopy using a Scanning Electron Microscopy confirmed that the inhomogeneity of the electrochemical oxidation process is increased by higher thicknesses and higher currents. A possible explanation is proposed to justify the different behavior of thin and thick samples during the electrochemical process. - Highlights: • A multidisciplinary approach on porous Si electrochemical oxidation is proposed. • Electrochemical, optical, and structural characterizations are used. • Layer thickness and oxidation current effects are shown. • An explanation of the observed behavior is proposed

  14. Mechanics of fluids in porous media

    Science.gov (United States)

    Bear, Jacob; Corapcioglu, M. Yavuz

    Transport of quantities such as mass component of a phase and/or heat occurs in fields as diversified as petroleum reservoir engineering, groundwater hydraulics, soil mechanics, industrial filtration, water purification, wastewater treatment, soil drainage and irrigation, and geothermal energy production. In all these areas, scientists, engineers, and planners make use of mathematical models; these models describe the relevant transport processes that occur within controlled porous medium domains and enable forecasting of the future behavior of these domains in response to planned activities. The mathematical models, in turn, are based on the understanding of phenomena, often within the void space, and on theories that relate these phenomena to measurable quantities.Because of the pressing needs in areas of practical interest such as the development of groundwater energy storage and geothermal energy production, a vast amount of research in all these fields has contributed, especially in the last two decades, to our understanding and ability to describe transport phenomena in porous media. In recent years these research efforts have been significantly accelerated, attracting scientists from many disciplines. The practical needs of solving boundary value problems in heterogeneous domains, irregular boundaries, coupled phenomena and multiple dependent variables led to the development of a variety of powerful numerical techniques. The realization that fields are highly heterogeneous and that the degree of heterogeneity depends on the scale of the problem led to the introduction of stochastic concepts as an additional tool for the description of phenomena.

  15. Statistical mechanics of unsaturated porous media

    Science.gov (United States)

    Xu, Jin; Louge, Michel Y.

    2015-12-01

    We explore a mean-field theory of fluid imbibition and drainage through permeable porous solids. In the limit of vanishing inertial and viscous forces, the theory predicts the hysteretic "retention curves" relating the capillary pressure applied across a connected domain to its degree of saturation in wetting fluid in terms of known surface energies and void space geometry. To avoid complicated calculations, we adopt the simplest statistical mechanics, in which a pore interacts with its neighbors through narrow openings called "necks," while being either full or empty of wetting fluid. We show how the main retention curves can be calculated from the statistical distribution of two dimensionless parameters λ and α measuring the specific areas of, respectively, neck cross section and wettable pore surface relative to pore volume. The theory attributes hysteresis of these curves to collective first-order phase transitions. We illustrate predictions with a porous domain consisting of a random packing of spheres, show that hysteresis strength grows with λ and weakens as the distribution of α broadens, and reproduce the behavior of Haines jumps observed in recent experiments on an ordered pore network.

  16. Static compression of porous dust aggregates

    Science.gov (United States)

    Kataoka, Akimasa; Tanaka, Hidekazu; Okuzumi, Satoshi; Wada, Koji

    2013-07-01

    To understand the structure evolution of dust aggregates is a key in the planetesimal formation. Dust grains become fluffy by coagulation in protoplanetary disks. However, once they become fluffy, they are not sufficiently compressed by collisional compression to form compact planetesimals (Okuzumi et al. 2012, ApJ, 752, 106). Thus, some other compression mechanisms are required to form planetesimals. We investigate the static compression of highly porous aggregates. First, we derive the compressive strength by numerical N-body simulations (Kataoka et al. 2013, A&A, 554, 4). Then, we apply the strength to protoplanetary disks, supposing that the highly porous aggregates can be quiasi-statically compressed by ram pressure of the disk gas and the self gravity. As a result, we find the pathway of the dust structure evolution from dust grains via fluffy aggregates to compact planetesimals. Moreover, we find that the fluffy aggregates overcome the barriers in planetesimal formation, which are radial drift, fragmentation, and bouncing barriers. (The paper is now available on arXiv: http://arxiv.org/abs/1307.7984 )

  17. Radiative heat transfer in porous uranium dioxide

    Energy Technology Data Exchange (ETDEWEB)

    Hayes, S.L. [Texas A and M Univ., College Station, TX (United States)

    1992-12-01

    Due to low thermal conductivity and high emissivity of UO{sub 2}, it has been suggested that radiative heat transfer may play a significant role in heat transfer through pores of UO{sub 2} fuel. This possibility was computationally investigated and contribution of radiative heat transfer within pores to overall heat transport in porous UO{sub 2} quantified. A repeating unit cell was developed to model approximately a porous UO{sub 2} fuel system, and the heat transfer through unit cells representing a wide variety of fuel conditions was calculated using a finite element computer program. Conduction through solid fuel matrix as wekk as pore gas, and radiative exchange at pore surface was incorporated. A variety of pore compositions were investigated: porosity, pore size, shape and orientation, temperature, and temperature gradient. Calculations were made in which pore surface radiation was both modeled and neglected. The difference between yielding the integral contribution of radiative heat transfer mechanism to overall heat transport. Results indicate that radiative component of heat transfer within pores is small for conditions representative of light water reactor fuel, typically less than 1% of total heat transport. It is much larger, however, for conditions present in liquid metal fast breeder reactor fuel; during restructuring of this fuel type early in life, the radiative heat transfer mode was shown to contribute as much as 10-20% of total heat transport in hottest regions of fuel.

  18. Statistical mechanics of unsaturated porous media.

    Science.gov (United States)

    Xu, Jin; Louge, Michel Y

    2015-12-01

    We explore a mean-field theory of fluid imbibition and drainage through permeable porous solids. In the limit of vanishing inertial and viscous forces, the theory predicts the hysteretic "retention curves" relating the capillary pressure applied across a connected domain to its degree of saturation in wetting fluid in terms of known surface energies and void space geometry. To avoid complicated calculations, we adopt the simplest statistical mechanics, in which a pore interacts with its neighbors through narrow openings called "necks," while being either full or empty of wetting fluid. We show how the main retention curves can be calculated from the statistical distribution of two dimensionless parameters λ and α measuring the specific areas of, respectively, neck cross section and wettable pore surface relative to pore volume. The theory attributes hysteresis of these curves to collective first-order phase transitions. We illustrate predictions with a porous domain consisting of a random packing of spheres, show that hysteresis strength grows with λ and weakens as the distribution of α broadens, and reproduce the behavior of Haines jumps observed in recent experiments on an ordered pore network. PMID:26764701

  19. Wave Interaction with Dual Circular Porous Plates

    Institute of Scientific and Technical Information of China (English)

    Arpita Mondal; R.Gayen

    2015-01-01

    In this paper we have investigated the reflection and the transmission of a system of two symmetric circular-arc-shaped thin porous plates submerged in deep water within the context of linear theory. The hypersingular integral equation technique has been used to analyze the problem mathematically. The integral equations are formulated by applying Green’s integral theorem to the fundamental potential function and the scattered potential function into a suitable fluid region, and then using the boundary condition on the porous plate surface. These are solved approximately using an expansion-cum-collocation method where the behaviour of the potential functions at the tips of the plates have been used. This method ultimately produces a very good numerical approximation for the reflection and the transmission coefficients and hydrodynamic force components. The numerical results are depicted graphically against the wave number for a variety of layouts of the arc. Some results are compared with known results for similar configurations of dual rigid plate systems available in the literature with good agreement.

  20. Recent Advances in Boron-Containing Conjugated Porous Polymers

    Directory of Open Access Journals (Sweden)

    Feng Qiu

    2016-05-01

    Full Text Available Porous polymers, integrating the advantages of porous materials and conventional polymers, have been well developed and exhibited tremendous attention in the fields of material, chemistry and biology. Of these, boron-containing conjugated porous polymers, featuring tunable geometric structures, unique Lewis acid boron centers and very rich physical properties, such as high specific surface, chargeable scaffold, strong photoluminescence and intramolecular charge transfer, have emerged as one of the most promising functional materials for optoelectronics, catalysis and sensing, etc. Furthermore, upon thermal treatment, some of them can be effectively converted to boron-doped porous carbon materials with good electrochemical performance in energy storage and conversion, extensively enlarging the applicable scope of such kinds of polymers. In this review, the synthetic approaches, structure analyses and various applications of the boron-containing conjugated porous polymers reported very recently are summarized.