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Exploring the Role of Inorganic and Organic Interfaces on CO 2 and CH 4 Partitioning: Case Study of Silica, Illite, Calcite, and Kerogen Nanopores on Gas Adsorption and Nanoscale Transport Behaviors
The adsorption, partitioning, and diffusion of CO 2 and CH 4 in organic–inorganic pores composed of kerogen with silica, illite, or calcite are studied using density functional theory and classical molecular dynamics simulations. The adsorption and partitioning behavior of CO 2 and CH 4 molecules is found to be a function of chemistry of the solid interface, pore size, and surface area. CO 2 molecules are preferentially adsorbed compared to CH 4 molecules on silica, illite, calcite, and kerogen surfaces due to significant contributions of electrostatic interactions with the atoms of the associated surfaces. CO 2 and CH 4 molecules display higher adsorption energy on calcite and silica compared to those on illite and kerogen because of enhanced interactions with the positively charged calcium ions on the calcite surface and the hydroxyl group (-OH) on the silica surface. Enhanced internal nanopores and the availability of adsorption active sites in illite and kerogen matrices aid in higher partitioning of the gas molecules into these pores. CO 2 has a significant influence on the clustering and swelling of kerogen fragments compared to CH 4 . Higher CO 2 adsorption on inorganic and kerogen surfaces results in lower overall self-diffusivities compared to CH 4 . This study illustrates surface and pore size controls on the adsorption, partitioning, and self-diffusivities of CO 2 and CH 4 at conditions relevant for subsurface energy applications. The chemistry of the surfaces along with the availability of internal pores and active adsorption sites influences the adsorption behavior of gases. Our results suggest that CO 2 stored in depleted gas reservoirs may preferentially inhabit nanoconfined pores.
Nanoscale Mg-Depleted Layers Slow Carbonation of Forsterite (Mg 2 SiO 4 ) When Water Is Limited
Passivation of silicate surfaces by accumulated reaction products is an obstacle to efficient CO 2 mineralization. In this study, we investigate a unique passivation effect during the carbonation of the basalt mineral forsterite (Mg 2 SiO 4 ) in humid supercritical CO 2 (50 °C, 90 bar). Using in situ high-pressure infrared spectroscopy, we demonstrate that dissolution of forsterite into a thin water film slows significantly after reaction for ˜24 h, even under far-from-equilibrium conditions. Further, 29 Si magic angle spinning nuclear magnetic resonance spectroscopy detects a highly polymerized amorphous silica at this stage. On the basis of transmission electron microscopy and energy dispersive X-ray spectroscopy, we show that the silica is present as a Mg-depleted layer that is just 2–3 nm thick on the reacted forsterite particles. The decrease in the level of forsterite dissolution in the presence of an extraordinarily thin Mg-depleted layer can be strongly linked to properties of the thin fluid film at the surface, highlighting the importance of water during mineral carbonation. This study furthers our understanding of silicate mineral carbonation under select low-water, humidified fluid conditions relevant to basaltic geologic reservoirs, recovery of critical elements by carbonation of mafic ores, and sequestration of atmospheric CO 2 by enhanced rock weathering.
Impact of Drying on Meso- and Nanoscale Structures of Citrus Fiber: A Study by SFG, ATR-IR, XRD, and DLS
Citrus fibers are a sidestream of the pectin extraction process from citrus peel. This sidestream can be converted into a functional ingredient through a shear-induced homogenization process. One technical challenge with this material is that dehydration and subsequent rehydration result in reduction of viscosity compared to the original product. In this study, various drying methods were compared with never-dried fibers to investigate the structural changes underlying the viscosity loss. Infrared and X-ray diffraction analyses confirmed no changes in chemical composition and crystalline structure of citrus fibers. Here, the dynamic light scattering and sum frequency generation analyses of citrus fiber suspension showed that the rehydration process could not fully disperse aggregated fibers, which appears to be the main cause for the viscosity loss.
Magnetic and Electrocatalytic Properties of Nanoscale Cobalt Boride, Co[subscript 3]B
Abstract not provided
Molecular Dynamics Investigation of Nanoscale Hydrophobicity of Polymer Surfaces: What Makes Water Wet?
The wettability of a polymer surface–related to its hydrophobicity or tendency to repel water–can be crucial for determining its utility, such as for a coating or a purification membrane. While wettability is commonly associated with the macroscopic measurement of a contact angle between surface, water, and air, the molecular physics that underlie these macroscopic observations are not fully known, and anticipating relative behavior of different polymers is challenging. To address this gap in molecular-level understanding, we use molecular dynamics simulations to investigate and contrast interactions of water with six chemically distinct polymers: polytetrafluoroethylene, polyethylene, polyvinyl chloride, poly(methyl methacrylate), Nylon 66, and polyvinyl alcohol. We show that several prospective quantitative metrics for hydrophobicity agree well with experimental contact angles. Moreover, the behavior of water in proximity to these polymer surfaces can be distinguished with analysis of interfacial water dynamics, extent of hydrogen bonding, and molecular orientation–even when macroscopic measures of hydrophobicity are similar. The predominant factor dictating wettability is found to be the extent of hydrogen bonding between polymer and water, but the precise manifestation of hydrogen bonding and its impact on surface-water structure varies. In the absence of hydrogen bonding, other molecular interactions and polymer mechanics control hydrophobic ordering. Furthermore, these results provide new insights into how polymer chemistry specifically impacts water-polymer interactions and translates to surface hydrophobicity. Such factors may facilitate the design or processing of polymer surfaces to achieve targeted wetting behavior, and presented analyses can be useful in studying the interfacial physics of other systems.
Fourier-like Thermal Relaxation of Nanoscale Explosive Hot Spots
Hot spots are local regions of high temperature that are widely considered to govern explosive initiation. Hot spot dynamics rests on a delicate balance between heat generation due to chemical reactions and heat loss through thermal conduction, making accurate determinations of the conductivity under extreme conditions a key component of predictive explosive models. We develop here an approach to directly determine the thermal transport properties of explosive hot spots with realistic initial structures through a combination of molecular dynamics (MD) and diffusive heat equation (HEq) modeling. Effective thermal conductivity values are determined by fitting HEq models to MD predictions of long timescale hot spot relaxation. The approach is applied to model hot spots in the molecular crystalline explosive 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) for a range of shock strengths and two limiting cases for impact orientation. Isotropic and anisotropic HEq models yield similar results, despite TATB exhibiting some of the largest and most anisotropic thermal conductivity values for explosive near normal conditions. The conductivity is found to be a strong function of density, which parametrically captures dependence on temperature, pressure, and material state. The associated root-mean-square errors of the fitted HEq models are approximately 5% of MD predicted final equilibrium temperatures. Here, the conductivity values determined here for TATB hot spots are considerably larger than those used in a prior hot spot criticality study, which may significantly impact predictions for critical hot spot sizes. The approach provides a convenient foundation for determining the effective thermal conductivity for hot spot problems in other explosives and directly yields information on reasonable approximations that might be taken in higher-level models for those materials.
Designing Highly Luminescent Molecular Aggregates via Bottom-Up Nanoscale Engineering
Not provided.
Frustrated Coulombic and Cation Size Effects on Nanoscale Boehmite Aggregation: A Tumbler Small- and Ultra-Small-Angle Neutron Scattering Study
To better understand the effects of solution chemistry on particle aggregation in the complex legacy tank wastes at the Hanford (WA) and Savannah River (SC) sites, we have performed a series of tumbler small- and ultra-small-angle neutron scattering experiments on 20 wt % solid slurries of nanoparticulate aluminum oxyhydroxide (boehmite) with M 1+ nitrates of various concentrations and radii. In this study, the solutes consisted of H, Li, Na, K, and Rb nitrates at 10 –5 , 10 –3 , 10 –1 , 2, and 4 molal (m) concentrations, as well as in pure H 2 O. Synthetic boehmite nanoparticles were used with a size range from ~20 to 30 nm. Tumbler cells were used to keep the solids from settling. Although particles initially form individual rhombohedral platelets, once placed in solution, they quickly form well-bonded stacks, primary aggregates, up to ~1500 Å long, and a second level of aggregates whose concentration and structure vary as a function of cation type and concentration. Aggregation generally increases with increased solute concentration and with cation radius up to a concentration somewhat above 10 –1 m, at which point the trend reverses. Primary aggregates become more rodlike and larger. The Kirkwood-like reversal probably reflects a change from Derjaguin–Landau–Verwey–Overbeek (DLVO)/Debye behavior controlled by surface chemistry to a frustrated Coulombic system controlled by the solution structure. These data suggest that an understanding of the effects of salt concentration and chemistry on nanoparticle aggregate structures provides useful physical insights into the microscopic origin of slurry rheology in the Hanford and Savannah River legacy wastes.
Exploring Critical Synthetic Parameters for Nanoscale ε-Fe 2 O 3 and Their Influence on Magnetic Behaviors
An intermediate polymorph of iron oxide, ε-Fe 2 O 3 , has attracted significant attention due to its giant coercive field ( H c ) and potential applications in high-frequency millimeter-wave absorption and high-density magnetic recording. However, the fabrication of ε-Fe 2 O 3 with high phase purity is still a challenge due to complicated synthetic procedures and a large variety of reaction parameters. In this study, we have identified critical reaction parameters to improve the phase purity of ε-Fe 2 O 3 , and the effects of all possible reaction parameters have been tested through systematic studies. A combination of structural and magnetic characterization techniques provides us with an accurate and reliable phase purity analysis of the ε-Fe 2 O 3 phase. Specifically, we observed that (1) the reaction temperature and time and (2) the addition of Ba are critical parameters to improve the phase purity. We identified the optimal conditions that maximize the coercivity and phase purity, giving insight into the effects of each parameter on the γ- to ε- to α-phase-transition pathway. We obtained nearly single-phase ε-Fe 2 O 3 (~87 wt % with ~13 wt % α-phase) with a large coercivity of H c = 20.6 kOe, enabling us to obtain pure ε-Fe 2 O 3 by a simple magnetic separation protocol, and tuned the H c of the ε-Fe 2 O 3 nanoparticles in the range of 4.0–20.6 kOe by controlling the reaction parameters. Furthermore, the structural properties of the resulting ε-Fe 2 O 3 nanoparticles are confirmed by characterizing their chemical and magnetic properties using X-ray absorption spectroscopy and X-ray magnetic circular dichroism measurements.
Nanoscale Relaxation in Water-in-Salt and Water-in-Bisalt Electrolytes
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Structural Anomalies and Electronic Properties of an Ionic Liquid under Nanoscale Confinement
Ionic liquids (ILs) promise far greater electrochemical performance compared to aqueous systems, yet key physicochemical properties governing their assembly at interfaces within commonly used graphitic nanopores remain poorly understood. Here, we combine synchrotron X-ray scattering with first-principles molecular dynamics simulations to unravel key structural characteristics of 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([TFSI] – ) ionic liquids confined in carbon slit pores. X-ray scattering reveals selective pore filling due to size exclusion, while filled pores exhibit disruption in the IL intermolecular structure, the extent of which increases for narrower slit pores. First-principles simulations corroborate this finding and quantitatively describe how perturbations in the local IL structure, particularly the hydrogen-bond network, depend strongly on the degree of confinement. Despite significant deviations in structure under confinement, electrochemical stability remains intact, which is important for energy storage based on nanoporous carbon electrodes (e.g., supercapacitors).
Nanoscale Photoexcited Carrier Dynamics in Perovskites
The optoelectronic properties of lead halide perovskite thin films can be tuned through compositional variations and strain, but the associated nanocrystalline structure makes it difficult to untangle the link between composition, processing conditions, and ultimately material properties and degradation. Here, we study the effect of processing conditions and degradation on the local photoconductivity dynamics in [(CsPbI 3 ) 0.05 (FAPbI 3 ) 0.85 (MAPbBr 3 ) 0.15 ] and (FA 0.7 Cs 0.3 PbI 3 ) perovskite thin films using temporally and spectrally resolved microwave near-field microscopy with a temporal resolution as high as 5 ns and a spatial resolution better than 50 nm. For the latter FACs formulation, we find a clear effect of the process annealing temperature on film morphology, stability, and spatial photoconductivity distribution. After exposure of samples to ambient conditions and illumination, we find spectral evidence of halide segregation-induced degradation below the instrument resolution limit for the mixed halide formulation, while we find a clear spatially inhomogeneous increase in the carrier lifetime for the FACs formulation annealed at 180 degrees C.