Moisture-driven carbonation kinetics for ultrafast CO mineralization.

CO mineralization, a process where CO reacts with minerals to form stable carbonates, presents a sustainable approach for CO sequestration and mitigation of global warming. While the crucial role of water in regulating CO mineralization efficiency is widely acknowledged, a comprehensive understanding of the underlying mechanisms remains elusive. This study employs a combined experimental and atomistic simulation approach to elucidate the intricate mechanisms governing moisture-driven carbonation kinetics of calcium-bearing minerals.

Optimal CO intake in metastable water film in mesoporous materials.

The feasibility of carbon mineralization relies on the carbonation efficiency of CO-reactive minerals, which is largely governed by the water content and state within material mesopores. Yet, the pivotal role of confined water in regulating carbonation efficiency at the nanoscale is not well understood. Here, we show that the maximum CO intake occurs at an optimal relative humidity (RH) when capillary condensation initiates within the hydrophilic mesopores.

Collective molecular-scale carbonation path in aqueous solutions with sufficient structural sampling: From CO2 to CaCO3.

The carbonation reaction is essential in the global carbon cycle and in the carbon dioxide (CO2) capture. In oceans (pH 8.1) or in synthetic materials such as cement or geopolymers (pH over 12), the basic pH conditions affect the reaction rate of carbonation.

Pressure and temperature diagram of C60 from atomistic simulations.

Although widely studied experimentally in the 1990s, the structure and properties of low-dimensional or high-pressure phases of fullerenes have recently been re-examined. Remarkably, recent experiments have shown that transparent, nearly pure amorphous sp3-bonded carbon phases can be obtained by heating a C60 molecular crystal at a high pressure. With the additional aim of testing the ability of three classical carbon potentials reactive empirical bond order, environment-dependent interatomic potential, and reactive force-field to reproduce these results, we investigate the details of the structural transformations undergone by fullerene crystals over a wide range of pressures and temperatures.

The Complex, Unique, and Powerful Imaging Instrument for Dynamics (CUPI2D) at the Spallation Neutron Source (invited).

The Oak Ridge National Laboratory is planning to build the Second Target Station (STS) at the Spallation Neutron Source (SNS). STS will host a suite of novel instruments that complement the First Target Station's beamline capabilities by offering an increased flux for cold neutrons and a broader wavelength bandwidth. A novel neutron imaging beamline, named the Complex, Unique, and Powerful Imaging Instrument for Dynamics (CUPI2D), is among the first eight instruments that will be commissioned at STS as part of the construction project.

Fluctuation-based fracture mechanics of heterogeneous materials.

We present results of a hybrid analytical-simulation investigation of the fracture resistance of heterogeneous materials. We show that bond-energy fluctuations sampled by Monte Carlo simulations in the semigrand canonical ensemble provide a means to rationalize the complexity of heterogeneous fracture processes, encompassing probability and percolation theories of fracture. For a number of random and textured model materials, we derive upper and lower bounds of fracture resistance and link bond fracture fluctuations to statistical descriptors of heterogeneity, such as two-point correlation functions, to identify the origin of toughening mechanisms.

Potential of Mean Force for Face-Face Interactions between Pairs of 2:1 Clay Mineral Platelets.

Bottom-up modeling of clay behavior from the molecular scale requires a detailed understanding of the free energy between pairs of clay platelets. We investigate the potential of mean force (PMF) for hydrated clays in face-to-face interactions with free energy perturbation (FEP) methods through molecular dynamics simulations using simple overlap sampling (SOS). We show that PMF results for open systems with one finite in-plane dimension are affected by migration of counterions from within the interlayer space compared with fully confined closed system conditions.

Ion Specificity of Confined Ion-Water Structuring and Nanoscale Surface Forces in Clays.

Ion specificity and related Hofmeister effects, which are ubiquitous in aqueous systems, can have spectacular consequences in hydrated clays, where ion-specific nanoscale surface forces can determine large-scale cohesive swelling and shrinkage behaviors of soil and sediments. We have used a semiatomistic computational approach and examined sodium, calcium, and aluminum counterions confined with water between charged surfaces representative of clay materials to show that ion-water structuring in nanoscale confinement is at the origin of surface forces between clay particles which are intrinsically ion-specific. When charged surfaces strongly confine ions and water, the amplitude and oscillations of the net pressure naturally emerge from the interplay of electrostatics and steric effects, which cannot be captured by existing theories.

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.

Condensation and growth of amorphous aluminosilicate nanoparticles an aggregation process.

The precipitation of zeolite nanoparticles involves the initial formation of metastable precursors, such as amorphous entities, that crystallize through non-classical pathways. Here, using reactive force field-based simulations, we reveal how aluminosilicate oligomers grow concomitantly to the decondensation of silicate entities during the initial step of the reaction. Aluminate clusters first form in the solution, thus violating the Loewenstein rule in the first instant of the reaction, which is then followed by their connection with silicate oligomers at the terminal silanol groups before reorganization to finally diffuse within the silicate oligomers to form stable amorphous aluminosilicate nanoparticles that do obey the Loewenstein rule.

Design of Binary NbO-SiO Self-Standing Monoliths Bearing Hierarchical Porosity and Their Efficient Friedel-Crafts Alkylation/Acylation Catalytic Properties.

Alkylation of aromatic hydrocarbons is among the most industrially important reactions, employing acid catalysts such as AlCl, HSO, HF, or HPO. However, these catalysts present severe drawbacks, such as low selectivity and high corrosiveness. Taking advantage of the intrinsic high acid strength and Lewis and Brønsted acidity of niobium oxide, we have designed the first series of NbO-SiO(HIPE) monolithic catalysts bearing multiscale porosity through the integration of a sol-gel process and the physical chemistry of complex fluids.

Theory of freezing point depression in charged porous media.

Freezing in charged porous media can induce significant pressure and cause damage to tissues and functional materials. We formulate a thermodynamically consistent theory to model freezing phenomena inside charged heterogeneous porous space. Two regimes are distinguished: free ions in open pore space lead to negligible effects of freezing point depression and pressure.

The physics of cement cohesion.

Cement is the most produced material in the world. A major player in greenhouse gas emissions, it is the main binding agent in concrete, providing a cohesive strength that rapidly increases during setting. Understanding how such cohesion emerges is a major obstacle to advances in cement science and technology.

Nanoscale Accessible Porosity as a Key Parameter Depicting the Topological Evolution of Organic Porous Networks.

A significant part of the hydrocarbons contained in source rocks remains confined within the organic matter-called kerogen-from where they are generated. Understanding the sorption and transport properties of confined hydrocarbons within the kerogens is, therefore, paramount to predict production. Specifically, knowing the impact of thermal maturation on the evolution of the organic porous network is key.

Phase diagram of brittle fracture in the semi-grand-canonical ensemble.

We present a simulation method to assess the quasistatic fracture resistance of materials. Set within a semi-grand-canonical Monte Carlo (SGCMC) simulation environment, an auxiliary field-the bond rupture potential-is introduced to generate a sufficiently large number of possible microstates in the semi-grand-canonical ensemble, and associated energy and bond fluctuations. The SGCMC approach permits identifying the full phase diagram of brittle fracture for harmonic and nonharmonic bond potentials, analogous to the gas-liquid phase diagram, with the equivalent of a liquidus line ending in a critical point.

Effect of Confinement on Capillary Phase Transition in Granular Aggregates.

Using a 3D mean-field lattice-gas model, we analyze the effect of confinement on the nature of capillary phase transition in granular aggregates with varying disorder and their inverse porous structures obtained by interchanging particles and pores. Surprisingly, the confinement effects are found to be much less pronounced in granular aggregates as opposed to porous structures. We show that this discrepancy can be understood in terms of the surface-surface correlation length with a connected path through the fluid domain, suggesting that this length captures the true degree of confinement.

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).

Effects of size polydispersity on random close-packed configurations of spherical particles.

We analyze the packing properties of simulated three-dimensional polydisperse samples of spherical particles assembled by mechanical compaction with zero interparticle friction, leading to random close-packed configurations of the highest packing fraction. The particle size distributions are generated from the incomplete beta distribution with three parameters: A size span and two shape parameters that control the curvature of the distribution function. For each size distribution, the number of particles is determined by accounting for the statistical representativity of all particle size classes in terms of both the numbers and volumes of particles.

Agglomeration of wet particles in dense granular flows.

In order to get insight into the wet agglomeration process, we numerically investigate the growth of a single granule inside a dense flow of an initially homogeneous distribution of wet and dry particles. The simulations are performed by means of the discrete element method and the binding liquid is assumed to be transported by the wet particles, which interact via capillary and viscous force laws. The granule size is found to be an exponential function of time, reflecting the conservation of the amount of liquid and the decrease of the number of available wet particles inside the flow during agglomeration.

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.

Multiscale poromechanics of wet cement paste.

Capillary effects, such as imbibition drying cycles, impact the mechanics of granular systems over time. A multiscale poromechanics framework was applied to cement paste, which is the most common building material, experiencing broad humidity variations over the lifetime of infrastructure. First, the liquid density distribution at intermediate to high relative humidity is obtained using a lattice gas density functional method together with a realistic nanogranular model of cement hydrates.

Capillary Stress and Structural Relaxation in Moist Granular Materials.

A numerical and theoretical framework to address the poromechanical effect of capillary stress in complex mesoporous materials is proposed and exemplified for water sorption in cement. We first predict the capillary condensation/evaporation isotherm using lattice-gas simulations in a realistic nanogranular cement model. A phase-field model to calculate moisture-induced capillary stress is then introduced and applied to cement at different water contents.

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.