Ab Initio Screening of Divalent Cations for CH4, CO2, H2, and N2 Separations in Chabazite Zeolite.

The efficient separation and adsorption of critical gases are, more than ever, a major focus point in important energy processes, such as CH4 enrichment of biogas or natural gas, CO2 separation and capture, and H2 purification and storage. Thanks to its physicochemical properties, cation-exchanged chabazite is a potent zeolite for such applications. Previous computational screening investigations have mostly examined chabazites exchanged with monovalent cations. Therefore, in this contribution, periodic density functional theory (DFT) calculations in combination with dispersion corrections have been used for a systematic screening of divalent cation exchanged chabazite zeolites. The work focuses on cheap and readily available divalent cations, Ca(II), Mg(II), and Zn(II), Fe(II), Sn(II), and Cu(II) and investigates the effect of the cation nature and location within the framework on the adsorption selectivity of chabazite for specific gas separations, namely, CO2/CH4, N2/CH4, and N2/H2. All the cationic adsorption sites were explored to describe the diversity of sites in a typical experimental chabazite with a Si/Al ratio close to 2 or 3. The results revealed that Mg-CHA is the most promising cation for the selective adsorption of CO2. These predictions were further supported by ab initio molecular dynamics simulations performed at 300 K, which demonstrated that the presence of CH4 has a negligible impact on the adsorption of CO2 on Mg-CHA. Ca(II) was found to be the most favorable cation for the selective adsorption of H2 and CO2. Finally, none of the investigated cations were suitable for the preferential capture of N2 and H2 in the purification of CH4 rich mixtures. These findings provide valuable insights into the factors influencing the adsorption behavior of N2, H2, CH4, and CO2 and highlight the crucial role played by theoretical calculations and simulations for the optimal design of efficient adsorbents.

Carbon-carbon supercapacitors: Beyond the average pore size or how electrolyte confinement and inaccessible pores affect the capacitance.

Carbon-carbon supercapacitors are high power electrochemical energy storage systems, which store energy through reversible ion adsorption at the electrode-electrolyte interface. Due to the complex structure of the porous carbons used as electrodes, extracting structure-property relationships in these systems remains a challenge. In this work, we conduct molecular simulations of two model supercapacitors based on nanoporous electrodes with the same average pore size, a property often used when comparing porous materials, but different morphologies. We show that the carbon with the more ordered structure, and a well defined pore size, has a much higher capacitance than the carbon with the more disordered structure and a broader pore size distribution. We analyze the structure of the confined electrolyte and show that the ions adsorbed in the ordered carbon are present in larger quantities and are also more confined than for the disordered carbon. Both aspects favor a better charge separation and thus a larger capacitance. In addition, the disordered electrodes contain a significant amount of carbon atoms, which are never in contact with the electrolyte, carry a close to zero charge, and are thus not involved in the charge storage. The total quantities of adsorbed ions and degrees of confinement do not change much with the applied potential, and as such, this work opens the door to computationally tractable screening strategies.

Ionic Liquids under Confinement: From Systematic Variations of the Ion and Pore Sizes toward an Understanding of the Structure and Dynamics in Complex Porous Carbons.

We use molecular simulations of an ionic liquid in contact with a range of nanoporous carbons to investigate correlations between the ion size, pore size, pore topology, and properties of the adsorbed ions. We show that diffusion coefficients increase with the anion size and, surprisingly, with the quantity of adsorbed ions. Both findings are interpreted in terms of confinement: when the in-pore population increases, additional ions are located in less-confined sites and diffuse faster. Simulations in which the pores are enlarged while keeping the topology constant support these observations. The interpretation of properties across structures is more challenging. An interesting point is that smaller pores do not necessarily lead to a larger confinement. In this work, the highest degrees of confinement are observed for intermediate pore sizes. We also show a correlation between the quantity of adsorbed ions and the ratio between the maximum pore diameter and the pore limiting diameter.