Crystalline metal-organic frameworks (MOFs) are formed by reticular synthesis, which creates strong bonds between inorganic and organic units. Careful selection of MOF constituents can yield crystals of ultrahigh porosity and high thermal and chemical stability. These characteristics allow the interior of MOFs to be chemically altered for use in gas separation, gas storage, and catalysis, among other applications. The precision commonly exercised in their chemical modification and the ability to expand their metrics without changing the underlying topology have not been achieved with other solids. MOFs whose chemical composition and shape of building units can be multiply varied within a particular structure already exist and may lead to materials that offer a synergistic combination of properties.

The Chemistry and Applications of Metal-Organic Frameworks

Deposits of clastic carbonate-dominated (calciclastic) sedimentary slope systems in the rock record have been identified mostly as linearly-consistent carbonate apron deposits, even though most ancient clastic carbonate slope deposits fit the submarine fan systems better. Calciclastic submarine fans are consequently rarely described and are poorly understood. Subsequently, very little is known especially in mud-dominated calciclastic submarine fan systems. Presented in this study are a sedimentological core and petrographic characterisation of samples from eleven boreholes from the Lower Carboniferous of Bowland Basin (Northwest England) that reveals a >250 m thick calciturbidite complex deposited in a calciclastic submarine fan setting. Seven facies are recognised from core and thin section characterisation and are grouped into three carbonate turbidite sequences. They include: 1) Calciturbidites, comprising mostly of highto low-density, wavy-laminated bioclast-rich facies; 2) low-density densite mudstones which are characterised by planar laminated and unlaminated muddominated facies; and 3) Calcidebrites which are muddy or hyper-concentrated debrisflow deposits occurring as poorly-sorted, chaotic, mud-supported floatstones. These

Phd by thesis

Kenji Sumida, David L. Rogow, Jarad A. Mason, Thomas M. McDonald, Eric D. Bloch, Zoey R. Herm, Tae-Hyun Bae, Jeffrey R. Long

Carbon Dioxide Capture in Metal–Organic Frameworks

2.2. MOFs with Metal Active Sites 4614 2.2.1. Early Studies 4614 2.2.2. Hydrogenation Reactions 4618 2.2.3. Oxidation of Organic Substrates 4620 2.2.4. CO Oxidation to CO2 4626 2.2.5. Phototocatalysis by MOFs 4627 2.2.6. Carbonyl Cyanosilylation 4630 2.2.7. Hydrodesulfurization 4631 2.2.8. Other Reactions 4632 2.3. MOFs with Reactive Functional Groups 4634 2.4. MOFs as Host Matrices or Nanometric Reaction Cavities 4636

Engineering Metal Organic Frameworks for Heterogeneous Catalysis

/pdf/metal-organic-frameworks-and-self-assembled-supramolecular-2xs948xxr9.pdf

Metal–Organic Frameworks and Self-Assembled Supramolecular Coordination Complexes: Comparing and Contrasting the Design, Synthesis, and Functionality of Metal–Organic Materials

The Dawson anion P2W18O626− has been used as a noncoordinating polyoxoanion template for the construction of two metal−organic frameworks, namely, [M2(bpy)3(H2O)2(ox)][P2W18O62]2(H2-bpy)·nH2O (M = Co(II), n = 3 (1); M = Ni(II), n = 2 (2)) (bpy = 4,4′-bipyridine; ox = C2O42−). Single-crystal X-ray analysis reveals that both of the structures exhibit 3D host frameworks constructed from the oxalate-bridged binuclear superoctahedron secondary building units (SBUs) and bpy linkers and the voids of which are occupied by Dawson anions, guest bpy, and water molecules. Magnetic studies reveal that there are antiferromagnetic exchange interactions among the transition-metal centers in compounds 1 and 2. Furthermore, a compound 1-modified carbon paste electrode (1-CPE) displays good electrocatalytic activity toward the reduction of nitrite.

Two Dawson-templated three-dimensional metal-organic frameworks based on oxalate-bridged binuclear cobalt(II)/Nickel(II) SBUs and Bpy linkers.

Solvothermal reactions with different solvents produced two iron trimesates [Fe2(H2O)2(BTC)4/3]Cl·4.5(DMF) (1) and [Fe4Cl(BTC)8/3]Cl2·H2O·2.5(DEF) (2) (BTC = 1,3,5-benzenetricarboxylate, DMF = N,N‘-dimethylformamide, DEF = N,N‘-diethylformamide). The framework of 1 is a (3,4)-connected net constructed from mixed-valence paddlewheel Fe2(II, III) units and BTC linkers, while the framework of 2 is a (3,8)-connected net built from mixed-valence square-planar Fe4(III, III, III, II) units and BTC linkers. The large volume inside the framework of 1 (or 2) is occupied by disordered Cl- anions and guest DMF (or DEF) molecules. The mixed-valence character of the frameworks of 1 and 2 was confirmed by Mossbauer spectroscopy studies. The active electronic property of iron cations may be the origin of the variability of the iron−organic frameworks, which are readily affected by some synthetic factors, such as solvents. Magnetic studies reveal that there are antiferromagnetic exchange interactions among the Fe atoms in...

Mixed-valence iron(II, III) trimesates with open frameworks modulated by solvents.

A series of organic–inorganic hybrid compounds, K2H7[{Ln(PW11O39)2}{Cu2(bpy)2(μ-ox)}]·xH2O (Ln = La, x≈ 18 (1); Ln = Pr, x≈ 18 (2); Ln = Eu, x≈ 16 (3); Ln = Gd, x≈ 22 (4); Ln = Yb, x≈ 19 (5); bpy = 2,2′-bipyridine and ox = oxalate), have been isolated by the conventional solution method. Single-crystal X-ray diffraction studies reveal that compounds 1–5 are isomorphic and consist of one-dimensional chains, which are constructed by alternating bis(undecatungstophosphate) lanthanates [Ln(PW11O39)2]11− and dinuclear copper(II)–oxalate complexes [Cu2(bpy)2(μ-ox)]2+. π–π interactions of the bpy ligands from adjacent chains lead to their three-dimensional structures. An analogue of potassium K2H9[{K(PW11O39)2}{Cu2(bpy)2(μ-ox)}]·∼20.5H2O (6) has also been obtained. The syntheses and structures of these compounds are reported here. Magnetic properties of 1, 2 and 3 are discussed as well. Attempts to crystallize similar compounds containing Co(II) and Ni(II) were unsuccessful.

Organic-inorganic hybrids assembled by bis(undecatungstophosphate) lanthanates and dinuclear copper(II)-oxalate complexes.

A unique porous 3D metal–organic framework has been synthesized based on the insertion of heterogeneous pillars between 2D layers, the permanent porosity of which is confirmed by N2 adsorption isotherm measurement.

Design and construction of a microporous metal–organic framework based on the pillared-layer motif

The solvothermal reactions of nickel nitrate hexahydrate, aromatic carboxylic acids, and either 4,4′-bipyridine (bipy) or pyrazine (pyz) produced three open-framework compounds, namely, Ni(HBTC)(pyz)·3DMF 2 (BTC = 1,3,5-benzentricarboxylate, DMF = N,N′-dimethylformamide), Ni2(BTEC)(bipy)3·3DMF 3 (BTEC = 1,2,4,5-benzenetetracarboxylate), together with previously reported Ni(HBTC)(bipy)·3DMF 1. Compound 2 is the product when pyz pillars replace bipy pillars in the reaction of 1, and it is a 3D porous network where honeycomb grid layers constructed by Ni-BTC groups are interlinked by pyz pillars. When the BTEC ligand takes the place of BTC ligand in the system, compound 3 is obtained and it is a 3D connectivity with 1D channels where Ni-BTEC chains are interlinked by bipy ligands. The three compounds feature permanent porosity, which was confirmed by N2 adsorption isotherm measurement, and the architectural features of 1–3 can be ascribed to pillared-layer motifs. Furthermore, hydrogen adsorption measured at 77 K for 1 shows an excess uptake of 3.03 wt% at 20 bar. Details of the synthesis conditions, crystal structures and property measurements of each new compound are described.

Chaoying Gao

Papers

Two Dawson-templated three-dimensional metal-organic frameworks based on oxalate-bridged binuclear cobalt(II)/Nickel(II) SBUs and Bpy linkers.

Mixed-valence iron(II, III) trimesates with open frameworks modulated by solvents.

Organic-inorganic hybrids assembled by bis(undecatungstophosphate) lanthanates and dinuclear copper(II)-oxalate complexes.

Design and construction of a microporous metal–organic framework based on the pillared-layer motif

Rational design microporous pillared-layer frameworks: syntheses, structures and gas sorption properties