Design of Covalent Organic Frameworks for Methane Storage

We designed 14 new covalent organic frameworks (COFs), which are expected to adsorb large amounts of methane (CH_4) at 298 K and up to 300 bar. We have calculated their delivery uptake using grand canonical Monte Carlo (GCMC) simulations. We also report their thermodynamic stability based on 7.5 ns molecular dynamics simulations. Two new frameworks, COF-103-Eth-trans and COF-102-Ant, are found to exceed the DOE target of 180 v(STP)/v at 35 bar for methane storage. Their performance is comparable to the best previously reported materials: PCN-14 and Ni-MOF-74. Our results indicate that using thin vinyl bridging groups aid performance by minimizing the interaction methane-COF at low pressure. This is a new feature that can be used to enhance loading in addition to the common practice of adding extra fused benzene rings. Most importantly, this report shows that pure nonbonding interactions, van der Waals (vdW) and electrostatic forces in light elements (C, O, B, H, and Si), can rival the enhancement in uptake obtained for microporous materials derived from early transition metals

Recent advances on simulation and theory of hydrogen storage in metal–organic frameworks and covalent organic frameworks

This critical review covers the application of computer simulations, including quantum calculations (ab initio and DFT), grand canonical Monte-Carlo simulations, and molecular dynamics simulations, to the burgeoning area of the hydrogen storage by metal–organic frameworks and covalent-organic frameworks. This review begins with an overview of the theoretical methods obtained from previous studies. Then strategies for the improvement of hydrogen storage in the porous materials are discussed in detail. The strategies include appropriate pore size, impregnation, catenation, open metal sites in metal oxide parts and within organic linker parts, doping of alkali elements onto organic linkers, substitution of metal oxide with lighter metals, functionalized organic linkers, and hydrogen spillover (186 references)

High H_2 Uptake in Li-, Na-, K-Metalated Covalent Organic Frameworks and Metal Organic Frameworks at 298 K

The Yaghi laboratory has developed porous covalent organic frameworks (COFs), COF102, COF103, and COF202, and metal–organic frameworks (MOFs), MOF177, MOF180, MOF200, MOF205, and MOF210, with ultrahigh porosity and outstanding H2 storage properties at 77 K. Using grand canonical Monte Carlo (GCMC) simulations with our recently developed first principles based force field (FF) from accurate quantum mechanics (QM), we calculated the molecular hydrogen (H2) uptake at 298 K for these systems, including the uptake for Li-, Na-, and K-metalated systems. We report the total, delivery and excess amount in gravimetric and volumetric units for all these compounds. For the gravimetric delivery amount from 1 to 100 bar, we find that eleven of these compounds reach the 2010 DOE target of 4.5 wt % at 298 K. The best of these compounds are MOF200-Li (6.34) and MOF200-Na (5.94), both reaching the 2015 DOE target of 5.5 wt % at 298 K. Among the undoped systems, we find that MOF200 gives a delivery amount as high as 3.24 wt % while MOF210 gives 2.90 wt % both from 1 to 100 bar and 298 K. However, none of these compounds reach the volumetric 2010 DOE target of 28 g H_2/L. The best volumetric performance is for COF102-Na (24.9), COF102-Li (23.8), COF103-Na (22.8), and COF103-Li (21.7), all using delivery g H_2/L units for 1–100 bar. These are the highest volumetric molecular hydrogen uptakes for a porous material under these thermodynamic conditions. Thus, one can obtain outstanding H_2 uptakes with Li, Na, and K doping of simple frameworks constructed from simple, cheap organic linkers. We present suggestions for strategies for synthesis of alkali metal-doped MOFs or COFs

Bound states in the continuum: localization of Dirac-like fermions

We report the formation of bound states in the continuum for Dirac-like fermions in structures composed by a trilayer graphene flake connected to nanoribbon leads. The existence of this kind of localized states can be proved by combining local density of states and electronic conductance calculations. By applying a gate voltage, the bound states couple to the continuum, yielding a maximum in the electronic transmission. This feature can be exploited to identify bound states in the continuum in graphene-based structures.Comment: 7 pages, 5 figure

Adsorption Mechanism and Uptake of Methane in Covalent Organic Frameworks: Theory and Experiment

We determined the methane (CH_4) uptake (at 298 K and 1 to 100 bar pressure) for a variety of covalent organic frameworks (COFs), including both two-dimensional (COF-1, COF-5, COF-6, COF-8, and COF-10) and three-dimensional (COF-102, COF-103, COF-105, and COF-108) systems. For all COFs, the CH_4 uptake was predicted from grand canonical Monte Carlo (GCMC) simulations based on force fields (FF) developed to fit accurate quantum mechanics (QM) [second order Møller−Plesset (MP2) perturbation theory using doubly polarized quadruple-ζ (QZVPP) basis sets]. This FF was validated by comparison with the equation of state for CH_4 and by comparison with the experimental uptake isotherms at 298 K (reported here for COF-5 and COF-8), which agrees well (within 2% for 1−100 bar) with the GCMC simulations. From our simulations we have been able to observe, for the first time, multilayer formation coexisting with a pore filling mechanism. The best COF in terms of total volume of CH_4 per unit volume COF absorbent is COF-1, which can store 195 v/v at 298 K and 30 bar, exceeding the U.S. Department of Energy target for CH_4 storage of 180 v/v at 298 K and 35 bar. The best COFs on a delivery amount basis (volume adsorbed from 5 to 100 bar) are COF-102 and COF-103 with values of 230 and 234 v(STP: 298 K, 1.01 bar)/v, respectively, making these promising materials for practical methane storage

Quantum critical behavior of electrons at the edge of charge order

We consider quantum critical points (QCP) in which quantum fluctuations associated with charge rather than magnetic order induce unconventional metallic properties. Based on finite-T calculations on a two-dimensional extended Hubbard model we show how the coherence scale T* characteristic of Fermi liquid behavior of the homogeneous metal vanishes at the onset of charge order. A strong effective mass enhancement reminiscent of heavy fermion behavior indicates the possible destruction of quasiparticles at the QCP. Experimental probes on quarter-filled layered organic materials are proposed for unveiling the behavior of electrons across the quantum critical region.Comment: 4 pages, 4 figures, accepted for publication in Phys. Rev. Let

Morphological characterisation of the coronary arteries in African sheep (Ovis orientalis). Differential analysis with those of humans and other animal species

Background: Despite the importance of the coronary system in the African sheep as a possible experimental model, there is little information about this particular vascular system. The objective of this investigation was to characterise morpho- logically the coronary arteries and their branches in African sheep.  Materials and methods: This descriptive cross-sectional study evaluated the coronary arteries and their branches of 62 hearts of short hair sheep. The right and left coronary ostia were perfused with a semi-synthetic resin (Palatal GP40L 85%; styrene 15%) dyed with mineral red. The morphological characteristics were evaluated using a digital calibrator and the biometrics of the coronary arteries and their branches were registered.  Results: The right coronary artery had a proximal calibre of 2.11 ± 0.46 mm. The subsinusal interventricular branch ended at the middle third of the homonym sulcus in 19 (30.6%) specimens. The left coronary artery had a diameter of 5.38 ± ± 1.59 mm and a length of 4.67 ± 3.32 mm. This artery bifurcated itself in the paraconal interventricular branch and the left circumflex branch in 57 (91.9%) hearts and trifurcated with an additional left diagonal branch in 5 (8.1%) spec- imens. Left coronary artery dominance was observed in 51 (82.3%) specimens, whereas in 11 (17.7%) cases the coronary circulation dominance was balanced.  Conclusions: Due to the similitude in the features of the coronary arteries between African sheep and humans, this animal model can be proposed for procedural and haemodynamic activities.