MOF-5 composites exhibiting improved thermal conductivity

Metal-organic frameworks MOF-5 Thermal conductivity Surface area a b s t r a c t The low thermal conductivity of the prototype hydrogen storage adsorbent, metal-organic framework 5 (MOF-5), can limit performance in applications requiring rapid gas uptake and release, such as in hydrogen storage for fuel cell vehicles. As a means to improve thermal conductivity, we have synthesized MOF-5-based composites containing 1e10 wt.% of expanded natural graphite (ENG) and evaluated their properties. Cylindrical pellets of neat MOF-5 and MOF-5/ENG composites with densities of 0.3, 0.5, and 0.7 g/cm 3 are prepared and assessed with regard to thermal conductivity, specific heat capacity, surface area, and crystallinity. For pellets of density w0.5 g/cm Copyright ª 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved. Introduction Metal-organic framework 5 (MOF-5) is a microporous, crystalline solid comprised of 1, Regarding gas storage, MOF-5 has been extensively studied for automotive hydrogen storage applications [1,7e10,15,16]. This interest stems from the observation that MOF-5 can adsorb a large amount of hydrogen, up to 7.1 excess wt.% at 77 K and 40 bar With conventional synthesis methods, MOF-5 is obtained as a loose powder consisting of small cubic crystallites (<1 mm) with low bulk density (r ¼ 0.13 g/cm 3 ) E-mail addresses: [email protected] (J. Yang), [email protected] (D.J. Siegel). Available online at www.sciencedirect.com journal h om epa ge: www.elsev ier.com/locate/he i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 6 1 0 9 e6 1 1

Surface nanobubbles as a function of gas type

We experimentally investigate the nucleation of surface nanobubbles on PFDTS-coated silicon as a function of the specific gas dissolved in the water. In each case we restrict ourselves to equilibrium conditions ($c=100$, $T_{liquid} = T_{substrate}$). Not only is nanobubble nucleation a strong function of gas type, but there also exists an optimal system temperature of $\sim 35-40\mathrm{^oC}$ where nucleation is maximized, which is weakly dependent on gas type. We also find that contact angle is a function of nanobubble radius of curvature for all gas types investigated. Fitting this data allows us to describe a line tension which is dependent on the type of gas, indicating that the nanobubbles are sat on top of adsorbed gas molecules. The average line tension was $\tau \sim -0.8 \mathrm{nN}$

Assembly of high nuclearity clusters from a family of tripodal tris-carboxylate ligands

A family of four tris-carboxylic acid ligands 1,3,5-tris(4′-carboxybiphenyl-2-yl)benzene (H3L1), 1,3,5-tris-2-carboxyphenylbenzene (H3L2), 1,3,5-tris(4″-carboxy-para-terphenyl-2-yl)benzene (H3L3) and 1,3,5-tris(3′-carboxybiphenyl-2-yl)benzene (H3L4) have been synthesised and reacted with first row transition metal cations to give nine complexes which have been structurally characterised by X-ray crystallography. The ligands share a common design motif having three arms connected to a benzene core via three ortho-disubstituted phenyl linkers. The ligands vary in length and direction of the carboxylic acid functionalised arms and are all able to adopt tripodal conformations in which the three arms are directed facially. The structures of [Zn8(μ4-O)(L1)4(HCO2)2(H2O)0.33(DMF)2] (1a-Zn), [Co14(L2)6((μ3-OH)8(HCO2)2(DMF)4(H2O)6] (2-Co), [Ni14(L2)6(μ3-OH)8(HCO2)2(DMF)4(H2O)6] (2-Ni), [Zn8(μ4-O)(L3)4(DMF)(H2O)4(NO3)2] (3-Zn), [Ni5(μ-OH)4(L2)2(H2O)6(DMF)4] (5-Ni), [Co8(μ4-O)4(L4)4(DMF)3(H2O)] (6-Co) and Fe3(μ3-O)(L4)2(H2O)(DMF)2)] (7-Fe) contain polynuclear clusters surrounded by ligands (L1–4)3− in tripodal conformations. The structure of [Zn2(HL1)2(DMF)4] (1b-Zn) shows it to be a binuclear complex in which the two ligands (HL2)2− are partially deprotonated whilst {[Zn3(L2)2(DMF)(H2O)(C5H5N)]·6(DMF)}n (4-Zn) is a 2D coordination network containing {Zn2(RCO2)4(solv)2} paddlewheel units. The conformations of the ligand arms in the complexes have been analysed, confirming that the shared ortho-disubstituted phenyl ring motif is a powerful and versatile tool for designing ligands able to form high-nuclearity coordination clusters when reacted with transition metal cations

Geometry analysis and systematic synthesis of highly porous isoreticular frameworks with a unique topology

Porous coordination polymers are well known for their easily tailored framework structures and corresponding properties. Although systematic modulations of pore sizes of binary prototypes have gained great success, simultaneous adjustment of both pore size and shape of ternary prototypes remains unexplored, owing to the difficulty in controlling the self-assembly of multiple molecular building blocks. Here we show that simple geometry analysis can be used to estimate the influence of the linker lengths and length ratios on the synthesis/construction difficulties and framework stabilities of a highly symmetric, ternary prototype composed of a typical trinuclear metal cluster and two types of bridging carboxylate ligands. As predicted, systematic syntheses with 5×5 ligand combinations produced 13 highly porous isoreticular frameworks, which show not only systematic adjustment of pore volumes (0.49–2.04 cm3 g−1) and sizes (7.8–13.0 Å; 5.2–12.0 Å; 7.4–17.4 Å), but also anisotropic modulation of the pore shapes

Follicular fluid content and oocyte quality: from single biochemical markers to metabolomics

The assessment of oocyte quality in human in vitro fertilization (IVF) is getting increasing attention from embryologists. Oocyte selection and the identification of the best oocytes, in fact, would help to limit embryo overproduction and to improve the results of oocyte cryostorage programs. Follicular fluid (FF) is easily available during oocyte pick-up and theorically represents an optimal source on non-invasive biochemical predictors of oocyte quality. Unfortunately, however, the studies aiming to find a good molecular predictor of oocyte quality in FF were not able to identify substances that could be used as reliable markers of oocyte competence to fertilization, embryo development and pregnancy. In the last years, a well definite trend toward passing from the research of single molecular markers to more complex techniques that study all metabolites of FF has been observed. The metabolomic approach is a powerful tool to study biochemical predictors of oocyte quality in FF, but its application in this area is still at the beginning. This review provides an overview of the current knowledge about the biochemical predictors of oocyte quality in FF, describing both the results coming from studies on single biochemical markers and those deriving from the most recent studies of metabolomic

Geometric requirements and examples of important structures in the assembly of square building blocks

The basic structures for linking squares into polyhedra and networks (reticulation) are enumerated, and corresponding examples are described in which crystals were synthesized by linking paddle wheel (square) units into metal–organic frameworks (MOFs)—named MOF-102 to MOF-112