How chemical defects influence the charging of nanoporous carbon supercapacitors.

SignificanceNanoporous carbon texture makes fundamental understanding of the electrochemical processes challenging. Based on density functional theory (DFT) results, the proposed atomistic approach takes into account topological and chemical defects of the electrodes and attributes to them a partial charge that depends on the applied voltage. Using a realistic carbon nanotexture, a model is developed to simulate the ionic charge both at the surface and in the subnanometric pores of the electrodes of a supercapacitor. Before entering the smallest pores, ions dehydrate at the external surface of the electrodes, leading to asymmetric adsorption behavior. Ions in subnanometric pores are mostly fully dehydrated. The simulated capacitance is in qualitative agreement with experiments. Part of these ions remain irreversibly trapped upon discharge.

Mesoscale structure, mechanics, and transport properties of source rocks' organic pore networks.

Organic matter is responsible for the generation of hydrocarbons during the thermal maturation of source rock formation. This geochemical process engenders a network of organic hosted pores that governs the flow of hydrocarbons from the organic matter to fractures created during the stimulation of production wells. Therefore, it can be reasonably assumed that predictions of potentially recoverable confined hydrocarbons depend on the geometry of this pore network. Here, we analyze mesoscale structures of three organic porous networks at different thermal maturities. We use electron tomography with subnanometric resolution to characterize their morphology and topology. Our 3D reconstructions confirm the formation of nanopores and reveal increasingly tortuous and connected pore networks in the process of thermal maturation. We then turn the binarized reconstructions into lattice models including information from atomistic simulations to derive mechanical and confined fluid transport properties. Specifically, we highlight the influence of adsorbed fluids on the elastic response. The resulting elastic energy concentrations are localized at the vicinity of macropores at low maturity whereas these concentrations present more homogeneous distributions at higher thermal maturities, due to pores' topology. The lattice models finally allow us to capture the effect of sorption on diffusion mechanisms with a sole input of network geometry. Eventually, we corroborate the dominant impact of diffusion occurring within the connected nanopores, which constitute the limiting factor of confined hydrocarbon transport in source rocks.

Timescale prediction of complex multi-barrier pathways using flux sampling molecular dynamics and 1D kinetic integration: Application to cellulose dehydration.

Reactive molecular dynamics (MD) simulations, especially those employing acceleration techniques, can provide useful insights on the mechanism underlying the transformation of buried organic matter, yet, so far, it remains extremely difficult to predict the time scales associated with these processes at moderate temperatures (i.e., when such time scales are considerably larger than those accessible to MD). We propose here an accelerated method based on flux sampling and kinetic integration along a 1D order parameter that can considerably extend the accessible time scales. We demonstrate the utility of this technique in an application to the dehydration of crystalline cellulose at temperatures ranging from 1900 K to 1500 K. The full decomposition is obtained at all temperatures apart from T = 1500 K, showing the same distribution of the main volatiles (H2O, CO, and CO2) as recently obtained using replica exchange molecular dynamics. The kinetics of the process is well fitted with an Arrhenius law with Ea = 93 kcal/mol and k0 = 9 × 1019 s-1, which are somehow larger than experimental reports. Unexpectedly, the process seems to considerably slow down at lower temperatures, severely departing from the Arrhenius regime, probably because of an inadequate choice of the order parameter. Nevertheless, we show that the proposed method allows considerable time sampling at low temperatures compared to conventional MD.

Poroelasticity of Methane-Loaded Mature and Immature Kerogen from Molecular Simulations.

While hydrocarbon expulsion from kerogen is certainly the key step in shale oil/gas recovery, the poromechanical couplings governing this desorption process, taking place under a significant pressure gradient, are still poorly understood. Especially, most molecular simulation investigations of hydrocarbon adsorption and transport in kerogen have so far been performed under the rigid matrix approximation, implying that the pore space is independent of pressure, temperature, and fluid loading, or in other words, neglecting poromechanics. Here, using two hydrogenated porous carbon models as proxies for immature and overmature kerogen, that is, highly aliphatic hydrogen-rich vs highly aromatic hydrogen-poor models, we perform an extensive molecular-dynamics-based investigation of the evolution of the poroelastic properties of those matrices with respect to temperature, external pressure, and methane loading as a prototype alkane molecule. The rigid matrix approximation is shown to hold reasonably well for overmature kerogen even though accounting for flexibility has allowed us to observe the well-known small volume contraction at low fluid loading and temperature. Our results demonstrate that immature kerogen is highly deformable. Within the ranges of conditions considered in this work, its density can double and its accessible porosity (to a methane molecule) can increase from 0 to ∼30%. We also show that these deformations are significantly nonaffine (i.e., nonhomogeneous), especially upon fluid adsorption or desorption.

Methane Diffusion in a Flexible Kerogen Matrix.

It has been recognized that the microporosity of shale organic matter, especially that of kerogen, strongly affects the hydrocarbon recovery process from unconventional reservoirs. So far, the numerical studies on hydrocarbon transport through the microporous phase of kerogen have neglected the effect of poromechanics, that is, the adsorption-induced deformations, by considering kerogen as a frozen, nondeformable, matrix. Here, we use molecular dynamics simulations to investigate methane diffusion in an immature (i.e., with high H/C ratio) kerogen matrix, while explicitly accounting for adsorption-induced swelling and internal matricial motions, covering both phonons and nonperiodic internal deformations. However, in the usual frozen matrix approximation, diffusivity decreases with increasing fluid loading, as evidenced by a loss of free volume, accounting for adsorption-induced swelling that gives rise to an increase in free volume and, hence, in diffusivity. The obtained trend is further rationalized using a Fujita-Kishimoto free volume theory initially developed in the context of diffusion in swelling polymers. We also quantify the enhancing effect of the matrix internal motions (i.e., at fixed volume) and show that it roughly gives an order of magnitude increase in diffusivity with respect to a frozen matrix, thanks to fluctuations in the pore connectivity. We eventually discuss the possible implications of this work to explain the productivity slowdown of hydrocarbon recovery from shale immature reservoirs.