The formation of methane hydrate in an unconsolidated bed of silica sand was investigated and spatially resolved by employing the magnetic resonance imaging technique. Different sand particle size ranges (210–297, 125–210, 88–177, and <75 μm) and different initial water saturations (100, 75, 50, and 25%) were used. It was observed that hydrate formation in such porous media is not uniform, and nucleation of hydrate crystals occurs at different times and different positions inside the bed. Also, hydrate formation was found to be faster in a bed with lower water content and smaller particle size. Decomposition of hydrate by thermal stimulation at constant volume showed that the dissociation front moves radially inward starting from the external surface of the hydrate formation vessel.

Heterobimetallic complexes of the formulations (NHC)Cu−FeCp(CO) 2 (NHC = IPr, IMes, SIMes), (IPr)Cu− MoCp(CO) 3 , and (IPr)(Cl)Zn−FeCp(CO) 2 were synthesized in high yield from readily available starting materials and characterized crystallographically. The solid-state structures of the Cu−Fe systems reveal close, secondary interactions between Cu and one CO ligand from the [FeCp(CO) 2 ] unit that are absent in the Zn−Fe analogue. The heterobimetallic complexes feature short yet polar Cu−Fe, Cu−Mo, and Zn−Fe bonds in which the electrophilic metal (Cu, Zn) is later in the transition series than the nucleophilic metal (Fe, Mo), thereby subverting the more common early−late heterobimetallic paradigm. DFT analyses were used to assess M−M′ bond polarity and examine effects on M−M′ bonding of systematic modifications to both the nucleophilic and electrophilic fragments. Experimental confirmation of Cu−Fe bond polarity was obtained by analysis of product mixtures resulting from the reactions between (NHC)Cu−FeCp(CO) 2 complexes and MeI, which produced (NHC)Cu−I and Me−FeCp(CO) 2 products.

Molecular dynamic simulations are performed to study the conditions for methane nano-bubble formation during methane hydrate dissociation in the presence of water and a methane gas reservoir. Hydrate dissociation leads to the quick release of methane into the liquid phase which can cause methane supersaturation. If the diffusion of methane molecules out of the liquid phase is not fast enough, the methane molecules agglomerate and form bubbles. Under the conditions of our simulations, the methane-rich quasi-spherical bubbles grow to become cylindrical with a radius of ∼11 Å. The nano-bubbles remain stable for about 35 ns until they are gradually and homogeneously dispersed in the liquid phase and finally enter the gas phase reservoirs initially set up in the simulation box. We determined that the minimum mole fraction for the dissolved methane in water to form nano-bubbles is 0.044, corresponding to about 30% of hydrate phase composition (0.148). The importance of nano-bubble formation to the mechanism of methane hydrate formation, growth, and dissociation is discussed.

We study the hydrated silica−water interface in the presence of methane or carbon dioxide gas with molecular dynamics simulations. The simulations are performed with a limited amount of water, which forms a meniscus between two hydroxylated silica surfaces separated by 40 to 60 Å. Simulations were performed with the remaining space of the simulation cell left empty or filled with different numbers of methane or carbon dioxide gas molecules. The meniscus is used to determine the contact angle between water and silica in the absence and presence of the gases. The distribution profiles of the water and gas phases are determined over the duration of the simulation. The water number density in the layers adjacent to the silica is higher, and these layers are more structured and less mobile compared with water layers far from the surface. Additionally, the concentrations of the gases are significantly higher at the liquid and silica interfaces than in other locations in the gas phase. We speculate that the enhanced concentration of gases at the interface along with the extended contact area (curved meniscus compared with flat interface in the absence of silica surfaces) between water and guest molecules at the meniscus as well as lesser mobility of water molecules near the silica surface may provide a mechanism for the heterogeneous nucleation of the clathrate hydrate in water-wetting porous medium.

Building upon the precedent of catalytically active (NHC)Cu-FeCp(CO)2 complexes, a series of (NHC)Cu-[M] complexes were synthesized via the addition of Na(+)[M](-) reagents to (NHC)CuCl synthons. The different [M](-) anions used span a range of 7 × 10(7) relative nucleophilicity units, allowing for controlled variation of nucleophile/electrophile pairing in the heterobimetallic species. Direct Cu-M bonds (M = Cr, Mn, Co, Mo, Ru, W) formed readily when the bulky IPr carbene was used as a support. Crystallographic characterization and computational examination of these complexes was conducted. For the smaller IMes carbene, structural isomerism was observed when using the weakest [M](-) nucleophiles, with (IMes)Cu-[M] and {(IMes)2Cu}{Cu[M]2} isomers being observed in equilibrium. Collectively, the series of complexes provides a toolbox for catalytic reaction discovery with precise control of structure-function relationships.

A tunable bimetallic effect on product selectivity in catalytic CO2 reduction was identified using N-heterocyclic carbene-ligated Cu complexes. While the monometallic Cu-only system catalyzes hydroboration of CO2 with pinacolborane to produce formate exclusively, introducing a bimetallic effect with analogous Cu-Fe, Cu-W, and Cu-Mo catalysts produces mixtures of formate and CO. Within a series of isosteric catalysts, the selectivity of CO versus formate was controlled by tuning the electronic nature of the Cu/M pairing, with high selectivity for CO being achieved using a Cu-Mo catalyst.

Antifreeze proteins (AFPs) prevent ice growth by binding to a specific ice plane. Some AFPs have been found to inhibit the formation of gas hydrates which are a serious safety and operational challenge for the oil and gas industry. Molecular dynamics simulations are used to determine the mechanism of action of the winter flounder AFP (wf-AFP) in inhibiting methane hydrate growth. The wf-AFP adsorbs onto the methane hydrate surface via cooperative binding of a set of hydrophobic methyl pendant groups to the empty half-cages at the hydrate/water interface. Each binding set is composed of the methyl side chain of threonine and two alanine residues, four and seven places further down in the sequence of the protein. Understanding the principle of action of AFPs can lead to the rational design of green hydrate inhibitor molecules with potential superior performance.

No abstract