Palladium Nanoparticles Supported on Ce-Metal–Organic Framework for Efficient CO Oxidation and Low-Temperature CO2 Capture

In this article, we report the lowest-temperature CO oxidation catalyst supported on metal–organic frameworks (MOFs). We have developed a facile, general, and effective approach based on microwave irradiation for the incorporation of Pd nanoparticle catalyst within Ce-MOF. The resulting Pd/Ce-MOF material is a unique catalyst that is capable of CO oxidation at modest temperatures and also of efficient uptake of the product CO2 gas at low temperatures. The observed catalytic activity of this material toward CO oxidation is significantly higher than those of other reported metal nanoparticles supported on MOFs. The high activity of the Pd/Ce-MOF catalyst is due to the presence of Ce(III) and Ce(IV) ions within the metal–organic framework support. The Pd nanoparticles supported on the Ce-MOF store oxygen in the form of a thin palladium oxide layer at the particle–support interface, in addition to the oxygen stored on the Ce(III)/Ce(IV) centers. Oxygen from these reservoirs can be released during CO oxidation at 373 K. At lower temperatures (273 K), the Pd/Ce-MOF has a significant CO2 uptake of 3.5 mmol/g

Highly porous photoluminescent diazaborole-linked polymers: synthesis, characterization, and application to selective gas adsorption

The formation of boron–nitrogen (B–N) bonds has been widely explored for the synthesis of small molecules, oligomers, or linear polymers; however, its use in constructing porous organic frameworks remains very scarce. In this study, three highly porous diazaborole-linked polymers (DBLPs) have been synthesized by condensation reactions using 2,3,6,7,14,15-hexaaminotriptycene and aryl boronic acids. DBLPs are microporous and exhibit high Brunauer–Emmett–Teller surface area (730–986 m2 g−1) which enable their use in small gas storage and separation. At ambient pressure, the amorphous polymers show high CO2 (DBLP-4: 4.5 mmol g−1 at 273 K) and H2 (DBLP-3: 2.13 wt% at 77 K) uptake while their physicochemical nature leads to high CO2/N2 (35–42) and moderate CO2/CH4 (4.9–6.2) selectivity. The electronic impact of integrating diazaborole moieties into the backbone of these polymers was investigated for DBLP-4 which exhibits green emission with a broad peak ranging from 350 to 680 nm upon excitation with 340 nm in DMF without photobleaching. This study demonstrates the effectiveness of B–N formation in targeting highly porous frameworks with promising optical properties

Covalent organic frameworks

The first members of covalent organic frameworks (COF) have been designed and successfully synthesized by condensation reactions of phenyl diboronic acid C6H4[B(OH)2]2 and hexahydroxytriphenylene C18H6(OH)6. The high crystallinity of the products (C3H2BO)6 (C9H12)1 (COF-1) and C9H4BO2 (COF-5) has allowed definitive resolution of their structure by powder X-ray diffraction methods which reveal expanded porous graphitic layers that are either staggered (COF-1, P63/mmc) or eclipsed (COF-5, P6/mmm). They exhibit high thermal stability (to temperatures up to 500- to 600-C), permanent porosity, and high surface areas (711 and 1590 m2/g, respectively) surpassing those of related inorganic frameworks. A similar approach has been used for the design of other extended structures

Metal-organic and covalent organic frameworks (MOFs and COFs) as adsorbents for environmentally significant gases (H2, CO2, and CH4)

A series of metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) possessing various functionalities, pore structures, and surface areas were evaluated for sorption and storage properties of environmentally significant gases (H_2, CO_2, and CH_4). It was concluded that the gas sorption behavior follows a general trend that materials with high surface area show enhanced gas uptake performance. For example, MOF-177 (SA = 5200 m^2/g) captures 7.2 wt% of H_2 at 77 K and 19 wt% of CH_4 at 298 K. In addition, MOF-177 exhibits exceptionally high gravimetric CO_2 uptake up to 120 wt% at 298 K. Similarly, the gas storage capacity for COFs seems to follow the same trend and it is determined by the apparent surface area. The architectural stability of both COFs and MOFs upon high pressure H_2 and CH_4 gas sorption measurements were manifested by isotherms which reach saturation without significant hysteresis

Designed Synthesis of 3D Covalent Organic Frameworks

Three-dimensional covalent organic frameworks (3D COFs) were synthesized by targeting two nets based on triangular and tetrahedral nodes: ctn and bor. The respective 3D COFs were synthesized as crystalline solids by condensation reactions of tetrahedral tetra(4-dihydroxyborylphenyl) methane or tetra(4-dihydroxyborylphenyl)silane and by co-condensation of triangular 2,3,6,7,10,11-hexahydroxytriphenylene. Because these materials are entirely constructed from strong covalent bonds (C-C, C-O, C-B, and B-O), they have high thermal stabilities (400° to 500°C), and they also have high surface areas (3472 and 4210 square meters per gram for COF-102 and COF-103, respectively) and extremely low densities (0.17 grams per cubic centimeter)

Covalently linked organic networks

In this review, we intend to give an overview of the synthesis of well-defined covalently bound organic network materials such as covalent organic frameworks, conjugated microporous frameworks, and other "ideal polymer networks" and discuss the different approaches in their synthesis and their potential applications. In addition we will describe the common computational approaches and highlight recent achievements in the computational study of their structure and properties. For further information, the interested reader is referred to several excellent and more detailed reviews dealing with the synthesis (Dawson et al., 2012; Ding andWang, 2013; Feng et al., 2012) and computational aspects (Han et al., 2009; Colón and Snurr, 2014) of the materials presented here

Polymer nanofilms with enhanced microporosity by interfacial polymerization

Highly permeable and selective membranes are desirable for energy-efficient gas and liquid separations. Microporous organic polymers have attracted significant attention in this respect owing to their high porosity, permeability, and molecular selectivity. However, it remains challenging to fabricate selective polymer membranes with controlled microporosity which are stable in solvents. Here we report a new approach to designing crosslinked, rigid polymer nanofilms with enhanced microporosity by manipulating the molecular structure. Ultra-thin polyarylate nanofilms with thickness down to 20 nm were formed in-situ by interfacial polymerisation. Enhanced microporosity and higher interconnectivity of intermolecular network voids, as rationalised by molecular simulations, are achieved by utilising contorted monomers for the interfacial polymerisation. Composite membranes comprising polyarylate nanofilms with enhanced microporosity fabricated in-situ on crosslinked polyimide ultrafiltration membranes show outstanding separation performance in organic solvents, with up to two orders of magnitude higher solvent permeance than membranes fabricated with nanofilms made from noncontorted planar monomers