Salvador R. G. Balestra

Atomic charges for modeling metal–organic frameworks: Why and how

Abstract Atomic partial charges are parameters of key importance in the simulation of Metal–Organic Frameworks (MOFs), since Coulombic interactions decrease with the distance more slowly than van der Waals interactions. But despite its relevance, there is no method to unambiguously assign charges to each atom, since atomic charges are not quantum observables. There are several methods that allow the calculation of atomic charges, most of them starting from the electronic wavefunction or the electronic density or the system, as obtained with quantum mechanics calculations. In this work, we describe the most common methods employed to calculate atomic charges in MOFs. In order to show the influence that even small variations of structure have on atomic charges, we present the results that we obtained for DMOF-1. We also discuss the effect that small variations of atomic charges have on the predicted structural properties of IRMOF-1.

Understanding Nanopore Window Distortions in the Reversible Molecular Valve Zeolite RHO

Molecular valves are becoming popular for potential biomedical applications. However, little is known concerning their performance in energy and environmental areas. Zeolite RHO shows unique pore deformations upon changes in hydration, cation siting, cation type, or temperature–pressure conditions. By varying the level of distortion of double eight-rings, it is possible to control the adsorption properties, which confer a molecular valve behavior to this material. We have employed interatomic potentials-based simulations to obtain a detailed atomistic view of the structural distortion mechanisms of zeolite RHO, in contrast with the averaged and space group restricted information provided by diffraction studies. We have modeled four aluminosilicate structures, containing Li+, Na+, K+, Ca2+ cations. The distortions of the three different zeolite rings are coupled, and the six- and eight-membered rings are largely flexible. A large dependence on the polarizing power of the extra-framework cations and with th...

Critical Role of Dynamic Flexibility in Ge‐Containing Zeolites: Impact on Diffusion

Abstract Incorporation of germanium in zeolites is well known to confer static flexibility to their framework, by stabilizing the formation of small rings. In this work, we show that the flexibility associated to Ge atoms in zeolites goes beyond this static effect, manifesting also a clear dynamic nature, in the sense that it leads to enhanced molecular diffusion. Our study combines experimental and theoretical methods providing evidence for this effect, which has not been described previously, as well as a rationalization for it, based on atomistic grounds. We have used both pure‐silica and silico‐germanate ITQ‐29 (LTA topology) zeolites as a case study. Based on our simulations, we identify the flexibility associated to the pore breathing‐like behavior induced by the Ge atoms, as the key factor leading to the enhanced diffusion observed experimentally in Ge‐containing zeolites.

Controlling Thermal Expansion: A Metal–Organic Frameworks Route

Controlling thermal expansion is an important, not yet resolved, and challenging problem in materials research. A conceptual design is introduced here, for the first time, for the use of metal–organic frameworks (MOFs) as platforms for controlling thermal expansion devices that can operate in the negative, zero, and positive expansion regimes. A detailed computer simulation study, based on molecular dynamics, is presented to support the targeted application. MOF-5 has been selected as model material, along with three molecules of similar size and known differences in terms of the nature of host–guest interactions. It has been shown that adsorbate molecules can control, in a colligative way, the thermal expansion of the solid, so that changing the adsorbate molecules induces the solid to display positive, zero, or negative thermal expansion. We analyze in depth the distortion mechanisms, beyond the ligand metal junction, to cover the ligand distortions, and the energetic and entropic effect on the thermo-structural behavior. We provide an unprecedented atomistic insight on the effect of adsorbates on the thermal expansion of MOFs as a basic tool toward controlling the thermal expansion.

Tuning the separation properties of zeolitic imidazolate framework core–shell structures via post-synthetic modification

The conversion of ZIF-8 into ZIF-7 via post-synthetic modification with benzimidazole has been monitored by quantifying the liberated 2-methylimidazole by chromatography. The reaction kinetics have been adjusted to the shrinking core model, providing the diffusion coefficient of bIm inside the pores and the reaction kinetic constant (2.86 × 10−7 cm2 s−1 and 1.36 × 10−4 cm s−1, respectively). A wide variety of ZIF-7/8 hybrid core–shell frameworks have been obtained during this reaction. The most promising have been characterized by SEM/TEM, TGA, N2 and CO2 adsorption, FTIR and 13C NMR, showing features of the coexistence of both phases inside the frameworks. Their structures have also been simulated, providing comparable XRD and adsorption results. The hybrid material has been used as a filler for PBI mixed matrix membranes (MMMs) applied to H2/CO2 separation, enhancing the performances of the bare PBI polymer and MMMs containing ZIF-8 or ZIF-7 as a filler, with a maximum H2 permeability value of 1921 Barrer and a H2/CO2 selectivity of 11.8.

Influence of Flexibility on the Separation of Chiral Isomers in STW-Type Zeolite

Molecular simulation, through the computation of adsorption isotherms, is a useful predictive tool for the selective capacity of nanoporous materials. Generally, adsorbents are modelled as rigid frameworks, as opposed to allowing for vibrations of the lattice, and this approximation is assumed to have negligible impact on adsorption. In this work, this approach was tested in an especially challenging system by computing the adsorption of the chiral molecules 2-pentanol, 2-methylbutanol and 3-methyl-2-butanol in the all-silica and germanosilicate chiral zeolites STW and studying their lattice vibrations upon adsorption. The analysis of single- and multicomponent adsorption isotherms showed the suitability of STW-type zeolites as molecular sieves for chiral separation processes, which pose a challenging task in the chemical and pharmaceutical industries. Moreover, new experimental adsorption data validate the force field employed. The results reveal that the lattice vibrations of the all-silica framework are sorbate-independent, while those of germanosilicate STW show host-guest coupling modulated by uptake and sorbate type that disrupts the chiral recognition sites. This study indicates that the effects of intrinsic flexibility on the selective capacity of nanoporous materials may range from low to high impact, and some of them could not have been foreseen even after examination of the structural dynamics of an empty framework.

The Si–Ge substitutional series in the chiral STW zeolite structure type

The whole compositional range (Gef = Ge/(Ge + Si) = 0 to 1) of zeolite STW has been synthesized and studied by a comprehensive combined experimental–theoretical approach. The yield of the zeolite goes through a maximum and then drops at the GeO2 side of the series, following the inverse of the calculated free energy curve. The unit cell generally expands, roughly linearly, as the Gef increases, but a notable resilience to expansion is observed at the high silica side. This can be attributed to the more rigid character of SiO2 and the ability of Ge units to deform. Density functional theory calculations provide a new assignment of the previously controversial 19F MAS NMR resonances for occluded fluoride, which is based not only on the number of Ge atoms in the double-4-ring units but also on the way they are associated (namely, no Ge, isolated Ge, Ge pairs or closed Ge clusters). While we found an overall good agreement between the experimental and theoretical trends in preferential occupation of different crystallographic sites by Ge, the theoretical models show more sharp and abrupt tendencies, likely due both to limitations of the approach and to kinetic factors that allow metastable configurations to actually exist.

Zeolites for CO2-CO-O2 separation to obtain CO2-neutral fuels

Carbon dioxide release has become an important global issue due to the significant and continuous rise in atmospheric CO2 concentrations and the depletion of carbon-based energy resources. Plasmolysis is a very energy-efficient process for reintroducing CO2 into energy and chemical cycles by converting CO2 into CO and O2 utilizing renewable electricity. The bottleneck of the process is that CO remains mixed with O2 and residual CO2. Therefore, efficient gas separation and recuperation are essential for obtaining pure CO, which, via water gas shift and Fischer-Tropsch reactions, can lead to the production of CO2-neutral fuels. The idea behind this work is to provide a separation mechanism based on zeolites to optimize the separation of carbon dioxide, carbon monoxide, and oxygen under mild operational conditions. To achieve this goal, we performed a thorough screening of available zeolites based on topology and adsorptive properties using molecular simulation and ideal adsorption solution theory. FAU, BRE, and MTW are identified as suitable topologies for these separation processes. FAU can be used for the separation of carbon dioxide from carbon monoxide and oxygen and BRE or MTW for the separation of carbon monoxide from oxygen. These results are reinforced by pressure swing adsorption simulations at room temperature combining adsorption columns with pure silica FAU zeolite and zeolite BRE at a Si/Al ratio of 3. These zeolites have the added advantage of being commercially available.