RESUMO
Adsorptive separations by nanoporous materials are major industrial processes. The industrial importance of solid adsorbents is only expected to grow due to the increased focus on carbon dioxide capture technology and energy-efficient separations. To evaluate the performance of an adsorbent and design a separation process, the adsorption thermodynamics and kinetics must be known. However, although diffusion kinetics determine the maximum production rate in any adsorption-based separation, this aspect has received less attention due to the challenges associated with conducting diffusion measurements. These challenges are exacerbated in the study of shaped adsorbents due to the presence of porosity at different length scales. As a result, adsorbent selection typically relies mainly on adsorption properties at equilibrium, i.e., uptake capacity, selectivity and adsorption enthalpy. In this Perspective, based on an extensive literature review on mass transfer of CO2 in nanoporous adsorbents, we discuss the importance and limitations of measuring diffusion in nanoporous materials, from the powder form to the adsorption bed, considering the nature of the process, i.e., equilibrium-based or kinetic-based separations. By highlighting the lack of and discrepancies between published diffusivity data in the context of CO2 capture, we discuss future challenges and opportunities in studying mass transfer across scales in adsorption-based separations.
RESUMO
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. Here, we propose an experimental procedure to study the interplay between the chemical evolution and the structural properties of the organic porous network at the nanometer scale. First, the organic porous networks of source rock samples, covering a significant range of natural thermal maturation experienced by the Vaca Muerta formation (Neuquén Basin, Argentina), are physically reconstructed using bright-field electron tomography. Their structural description allows us to measure crucial parameters such as the porosity, specific pore volume and surface area, aperture and cavity size distributions, and constriction. In addition, a model-free computation of the topological properties (effective porosity, connectivity, and tortuosity) is conducted. Overall, we document a general increase of the specific pore volume with thermal maturation. This controls the topological features depicting increasing accessibility to alkane molecules, sensed by the evolution of the effective porosity. Collectively, our results highlight the input of bright-field electron tomography in the study of complex disordered amorphous porous media, especially to describe the interplay between the structural features and transport properties of confined fluids.
RESUMO
Single-walled carbon nanotubes are hollow cylinders that can grow centimeters long via carbon incorporation at the interface with a catalyst. They display semiconducting or metallic characteristics, depending on their helicity, which is determined during their growth. To support the quest for a selective synthesis, we develop a thermodynamic model that relates the tube-catalyst interfacial energies, temperature, and the resulting tube chirality. We show that nanotubes can grow chiral because of the configurational entropy of their nanometer-sized edge, thus explaining experimentally observed temperature evolutions of chiral distributions. Taking the chemical nature of the catalyst into account through interfacial energies, we derive structural maps and phase diagrams that will guide a rational choice of a catalyst and growth parameters toward a better selectivity.
RESUMO
Chemical vapor deposition synthesis of single-walled carbon nanotubes, using an Fe catalyst, and alternating methane and carbon monoxide as carbon feedstocks, leads to the reversible formation of junctions between tubes of different diameters. Combined with an atomistic modeling of the tube/catalyst interface, this shows that the ratio of diameters of the tube and its seeding particle, denoting the growth mode, depends on the carbon fraction inside the catalyst. With carbon monoxide, nanoparticles are strongly carbon enriched, and tend to dewet the tube, in a perpendicular growth mode. Cross-checking our results with the available reports from the literature of the last decade strongly suggests that these latter conditions should favor the near armchair chiral selectivity observed empirically.
RESUMO
Structural identification of double-walled carbon nanotubes (DWNTs) is presented through a robust procedure based on the latest generation of transmission electron microscope, making possible a statistical analysis based on numerous nano-objects. This approach reveals that inner and outer tubes of DWNTs are not randomly oriented, suggesting the existence of a mechanical coupling between the two concentric walls. With the support of atomic-scale modeling, we attribute it to the presence of incommensurate domains whose structures depend on the diameters and helicities of both tubes and where inner tubes try to achieve a local stacking orientation to reduce strain effects.