Reticular chemistry: occurrence and taxonomy of nets and grammar for the design of frameworks

The structures of all 1127 three-periodic extended metal-organic frameworks (MOFs) reported in the Cambridge Structure Database have been analyzed, and their underlying topology has been determined. It is remarkable that among the almost infinite number of net topologies that are available for MOFs to adopt, only a handful of nets are actually observed. The discovery of this inversion between expected and observed nets led us to deduce a system of classification "taxonomy" for interpreting and rationalizing known MOF structures, as well as those that will be made in future. The origin of this inversion is attributed to the different modes with which MOF synthesis has been approached. Specifically, three levels of complexity are defined that embody rules "grammar" for the design of MOFs and other extended structures. This system accounts for the present proliferation of MOF structures of high symmetry nets, but more importantly, it provides the basis for designing a building block that "codes" for a specific structure and, indeed, only that structure.     

Zeolite A imidazolate frameworks

Faujasite (FAU) and zeolite A (LTA) are technologically important porous zeolites (aluminosilicates) because of their extensive use in petroleum cracking and water softening. Introducing organic units and transition metals into the backbone of these types of zeolite allows us to expand their pore structures, enhance their functionality and access new applications. The invention of metal-organic frameworks and zeolitic imidazolate frameworks (ZIFs) has provided materials based on simple zeolite structures where only one type of cage is present. However, so far, no metal-organic analogues based on FAU or LTA topologies exist owing to the difficulty imposed by the presence of two types of large cage (super- and beta-cages for FAU, alpha- and beta-cages for LTA). Here, we have identified a strategy to produce an LTA imidazolate framework in which both the link geometry and link-link interactions play a decisive structure-directing role. We describe the synthesis and crystal structures of three porous ZIFs that are expanded analogues of zeolite A; their cage walls are functionalized, and their metal ions can be changed without changing the underlying LTA topology. Hydrogen, methane, carbon dioxide and argon gas adsorption isotherms are reported and the selectivity of this material for carbon dioxide over methane is demonstrated.     

Design and synthesis of metal-carboxylate frameworks with permanent microporosity

Metal-carboxylate clusters are ideally suited as secondary building units (SBU) for the assembly of extended open frameworks. Examples extracted from the chemistry of the multidentate building block 1,4-benzenedicarboxylate (BDC) show that Zn(BDC) clusters lead to the formation of rigid, stable and truly microporous metal-carboxylate networks. Gas sorption isotherms measured for this class of materials show type (I) gas uptake that is analogous to those observed for zeolites and molecular sieves. This revised version was published online in August 2006 with corrections to the Cover Date.     

Local Electronic Structure of Molecular Heterojunctions in a Single‐Layer 2D Covalent Organic Framework

The synthesis of a single‐layer covalent organic framework (COF) with spatially modulated internal potentials provides new opportunities for manipulating the electronic structure of molecularly defined materials. Here, the fabrication and electronic characterization of COF‐420: a single‐layer porphyrin‐based square‐lattice COF containing a periodic array of oriented, type II electronic heterojunctions is reported. In contrast to previous donor–acceptor COFs, COF‐420 is constructed from building blocks that yield identical cores upon reticulation, but that are bridged by electrically asymmetric linkers supporting oriented electronic dipoles. Scanning tunneling spectroscopy reveals staggered gap (type II) band alignment between adjacent molecular cores in COF‐420, in agreement with first‐principles calculations. Hirshfeld charge analysis indicates that dipole fields from oriented imine linkages within COF‐420 are the main cause of the staggered electronic structure in this square grid of atomically–precise heterojunctions.     

Modular chemistry: secondary building units as a basis for the design of highly porous and robust metal-organic carboxylate frameworks

Secondary building units (SBUs) are molecular complexes and cluster entities in which ligand coordination modes and metal coordination environments can be utilized in the transformation of these fragments into extended porous networks using polytopic linkers (1,4-benzenedicarboxylate, 1,3,5,7-adamantanetetracarboxylate, etc.). Consideration of the geometric and chemical attributes of the SBUs and linkers leads to prediction of the framework topology, and in turn to the design and synthesis of a new class of porous materials with robust structures and high porosity.     

Analysis of aflatoxin M1 in milk and yogurt and AFM1 reduction by lactic acid bacteria used in Lebanese industry

In this study a screening survey was undertaken to determine the presence and levels of aflatoxin M1 (AFM1) in locally produced dairy products. For this purpose, a total of 138 dairy samples (milk and yogurt) were analyzed to quantify AFM1 levels in these products. Results obtained showed that AFM1 was found in 40.62% and 32.81% of milk and yogurt samples respectively. The range of contamination levels varied between lower and higher than European regulation limit. Lactic acid bacteria (Lactobacillus bulgaricus and Streptococcus thermophilus) used in the Lebanese traditional industry were screened for their ability to reduce the level of AFM1. Due to the lack in data on the natural occurrence of AFM1 in Lebanese dairy products, the aim of this work was to report some information and to state these products according to EC regulations     

MOF-74 building unit has a direct impact on toxic gas adsorption

Metal organic framework (MOF-74) analogs have been synthesized using cobalt, magnesium, nickel, and zinc metal centers. The capability of these materials to remove ammonia, cyanogen chloride, and sulfur dioxide from air has been evaluated via fixed-bed breakthrough testing in both dry and humid conditions. Octane breakthrough tests were performed to determine the physisorption capacities of the materials. All materials were stored in air prior to use. Dynamic breakthrough capacities of the analogs were compared to 13X zeolite and BPL activated carbon. The impact of the metal center on the adsorption behavior is illustrated with each analog providing different ammonia and cyanogen chloride adsorption capacities. The results provide an important step in the assessment of the potential of MOFs to function as porous adsorbent materials.     

Assessment of alternative management techniques of tank bottom petroleum sludge in Oman

This paper investigated several options for environmentally acceptable management techniques of tank bottom oily sludge. In particular, we tested the applicability of managing the sludge by three options: (1) as a fuel supplement; (2) in solidification; (3) as a road material. Environmental testing included determination of heavy metals concentration; toxic organics concentration and radiological properties. The assessment of tank bottom sludge as a fuel supplement included various properties such as proximate analysis, ultimate analysis and energy content. Solidified sludge mixtures and road application sludge mixtures were subjected to leaching using the toxicity characteristic leaching procedure (TCLP). Tank bottom sludge was characterized as having higher concentrations of lead, zinc, and mercury, but lower concentrations of nickel, copper and chromium in comparison with values reported in the literature. Natural occurring radioactive minerals (NORM) activity values obtained on different sludge samples were very low or negligible compared to a NORM standard value of 100Bq/g. The fuel assessment results indicate that the heating values, the carbon content and the ash content of the sludge samples are comparable with bituminous coal, sewage sludge, meat and bone meal and petroleum coke/coal mixture, but lower than those in car tyres and petroleum coke. The nitrogen content is lower than those fuels mentioned above, while the sulfur content seems comparable with bituminous coal, petroleum coke and a petroleum coke/coal mixture. The apparent lack of leachability of metals from solidification and road material sludge applications suggests that toxic metals and organics introduced to these applications are not readily attacked by weak acid solutions and would not be expected to migrate or dissolved into the water. Thus, in-terms of trace metals and organics, the suggested sludge applications would not be considered hazardous as defined by the TCLP leaching procedure.