The influence of finite size in altering the phase stabilities of strongly correlated materials gives rise to the interesting prospect of achieving additional tunability of solid-solid phase transitions such as those involved in metal-insulator switching, ferroelectricity, and superconductivity. We note here some distinctive finite size effects on the relative phase stabilities of insulating (monoclinic) and metallic (tetragonal) phases of solid-solution W x V 1Àx O 2 . Ensemble differential scanning calorimetry and individual nanobelt electrical transport measurements suggest a pronounced hysteresis between metal / insulator and insulator / metal phase transformations. Both transitions are depressed to lower critical temperatures upon the incorporation of substitutional tungsten dopants but the impact on the former transition seems far more prominent. In general, the depression in the critical temperatures upon tungsten doping far exceeds corresponding values for bulk W x V 1Àx O 2 of the same composition. Notably, the depression in phase transition temperature saturates at a relatively low dopant concentration in the nanobelts, thought to be associated with the specific sites occupied by the tungsten substitutional dopants in these structures. The marked deviations from bulk behavior are rationalized in terms of a percolative model of the phase transition taking into account the nucleation of locally tetragonal domains and enhanced carrier delocalization that accompany W 6+ doping in the W x V 1Àx O 2 nanobelts.

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Metal-insulator transitions in strongly correlated materials, induced by varying either temperature or dopant concentration, remain a topic of enduring interest in solid-state chemistry and physics owing to their fundamental importance in answering longstanding questions regarding correlation effects. We note here the unprecedented observation of a four-orders-of-magnitude metal-insulator transition in single nanowires of delta-K(x)V(2)O(5), when temperature is varied, which thus represents a rare new addition to the pantheon of materials exhibiting pronounced metal-insulator transitions in proximity to room temperature.

Given the complex nature of the interaction between gas and solid atoms, the development of nanoscale science and technology has engendered a need for further understanding of gas transport behavior through nanopores and more tractable models for large-scale simulations. In the present paper, we utilize molecular dynamic simulations to demonstrate the behavior of gas flow under the influence of adsorption in nano-channels consisting of illite and graphene, respectively. The results indicate that velocity oscillation exists along the cross-section of the nano-channel, and the total mass flow could be either enhanced or reduced depending on variations in adsorption under different conditions. The mechanisms can be explained by the extra average perturbation stress arising from density oscillation via the novel perturbation model for micro-scale simulation, and approximated via the novel dual-region model for macro-scale simulation, which leads to a more accurate permeability correction model for industrial applications than is currently available.

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We investigate the flow of methane in a kerogen matrix with microstructural flexibilities at various pressures. The matrix is constructed by compressing a collection of 60 type II kerogen macromolecules. In the past, simulations of methane flow in kerogen matrices have been performed assuming rigid molecular structures. We extend the simulations from rigid molecules to flexible molecules. The gas flow simulations are performed based on the boundary-driven method. We introduce a limited number of virtual “nails” to keep the flexible kerogen matrix in place. It is demonstrated that the flexibility of the kerogen microstructure has a significant effect on gas diffusion, which is the primary transport mechanism in kerogen that contains micropores. The adsorption in flexible kerogen is higher than in rigid kerogen. Adsorption in flexible kerogen matrix may narrow the main flow path and reduce gas flow in the confined environment under subsurface conditions. On the other hand, the occasional opening of pore throats in the flexible kerogen matrix can provide additional flux. We find that the transport of methane in flexible kerogen is less than that in rigid kerogen due to changes in pore shape, despite the additional transport from pore opening in the flexible kerogen matrix.