A new software package, RASPA, for simulating adsorption and diffusion of molecules in flexible nanoporous materials is presented. The code implements the latest state-of-the-art algorithms for ...molecular dynamics and Monte Carlo (MC) in various ensembles including symplectic/measure-preserving integrators, Ewald summation, configurational-bias MC, continuous fractional component MC, reactive MC and Baker's minimisation. We show example applications of RASPA in computing coexistence properties, adsorption isotherms for single and multiple components, self- and collective diffusivities, reaction systems and visualisation. The software is released under the GNU General Public License.
Selective separation of enantiomers is a substantial challenge for the pharmaceutical industry. Chromatography on chiral stationary phases is the standard method, but at a very high cost for ...industrial-scale purification due to the high cost of the chiral stationary phases. Typically, these materials are poorly robust, expensive to manufacture, and often too specific for a single desired substrate, lacking desirable versatility across different chiral analytes. Here, we disclose a porous, robust homochiral metal–organic framework (MOF), TAMOF-1, built from copper(II) and an affordable linker prepared from natural l-histidine. TAMOF-1 has shown to be able to separate a variety of model racemic mixtures, including drugs, in a wide range of solvents of different polarity, outperforming several commercial chiral columns for HPLC separations. Although not exploited in the present article, it is worthy to mention that the preparation of this new material is scalable to the multikilogram scale, opening unprecedented possibilities for low-energy chiral separation at the industrial scale.
The commercialization of perovskite solar cells is hindered by the poor long-term stability of the metal halide perovskite (MHP) light-absorbing layer. Solution processing, the common fabrication ...method for MHPs, produces polycrystalline films with a wide variety of defects, such as point defects, surfaces, and grain boundaries. Although the optoelectronic effects of such defects have been widely studied, the evaluation of their impact on the long-term stability remains challenging. In particular, an understanding of the dynamics of degradation reactions at the atomistic scale is lacking. In this work, using reactive force field (ReaxFF) molecular dynamics simulations, we investigate the effects of defects, in the forms of surfaces, surface defects, and grain boundaries, on the stability of the inorganic halide perovskite CsPbI3. Our simulations establish a stability trend for a variety of surfaces, which correlates well with the occurrence of these surfaces in experiments. We find that a perovskite surface degrades by progressively changing the local geometry of PbI x octahedra from corner- to edge- to face-sharing. Importantly, we find that Pb dangling bonds and the lack of steric hindrance of I species are two crucial factors that induce degradation reactions. Finally, we show that the stability of these surfaces can be modulated by adjusting their atomistic details, by either creating additional point defects or merging them to form grain boundaries. While in general additional defects, particularly when clustered, have a negative impact on the material stability, some grain boundaries have a stabilizing effect, primarily because of the additional steric hindrance.
We performed molecular simulations to investigate the adsorption and diffusion of benzene in metal–organic framework Mg-MOF-74. At 300 K and 20 Pa, the saturated loading of benzene reaches 8.2 ...mmol/g, almost twice of (12,12) single-walled carbon nanotube with a similar pore size, and 93% of the benzene molecules in Mg-MOF-74 can desorb at 390 K. The energy analysis indicates that the van der Waals contribution still dominates 70–80% of the total fluid–wall interaction energy compared with the Coulombic contribution. We further analyzed the structure of benzene confined in Mg-MOF-74 by the molecular snapshots, pair correlation functions, orientational order parameters, and local density profiles. It is found that low temperature and high pressure make the structure of adsorbed benzene more similar to that of the liquid benzene. Moreover, the benzene molecules in the contact adsorption layer lie flat on the surface of adsorbent, whereas those molecules near the pore center have no particular orientations. Due to the existence of open metal sites, the structures of adsorbed benzene are more compact and ordered than those of bulk liquid benzene. Consequently, the self-diffusion coefficient of saturated benzene in Mg-MOF-74 at 300 K is significantly lower than that of bulk liquid benzene and confined liquid benzene in slit pores and disordered carbons by 4–5 orders of magnitude. We investigated the separation and diffusion of benzene/cyclohexane in the mixture in Mg-MOF-74 and found that the pores almost completely adsorbed benzene, although its self-diffusion coefficient was slightly lower than that of cyclohexane.
All-inorganic halide perovskites have received a great deal of attention as attractive alternatives to overcome the stability issues of hybrid halide perovskites that are commonly associated with ...organic cations. To find a compromise between the optoelectronic properties of CsPbI3 and CsPbBr3, perovskites with CsPb(Br x I1–x )3 mixed compositions are commonly used. An additional benefit is that without sacrificing the optoelectronic properties for applications such as solar cells or light-emitting diodes, small amounts of Br in CsPbI3 can prevent the inorganic perovskite from degrading to a photo-inactive non-perovskite yellow phase. Despite indications that strain in the perovskite lattice plays a role in the stabilization of the material, a full understanding of such strain is lacking. Here, we develop a reactive force field (ReaxFF) for perovskites starting from our previous work for CsPbI3, and we extend this force field to CsPbBr3 and mixed CsPb(Br x I1–x )3 compounds. This force field is used in large-scale molecular dynamics simulations to study perovskite phase transitions and the internal ion dynamics associated with the phase transitions. We find that an increase of the Br content lowers the temperature at which the perovskite reaches a cubic structure. Specifically, by substituting Br for I, the smaller ionic radius of Br induces a strain in the lattice that changes the internal dynamics of the octahedra. Importantly, this effect propagates through the perovskite lattice ranging up to distances of 2 nm, explaining why small concentrations of Br in CsPb(Br x I1–x )3 (x ≤ 1/4) have a significant impact on the phase stability of mixed halide perovskites.
Molecular simulations were performed to study the adsorption behavior of water in the metal−organic framework Cu−BTC. This is one of the better-known materials of this type that is stable upon water ...adsorption/desorption. The charge of the framework atoms was fitted to reproduce the available experimental adsorption isotherm. This new set of interaction parameters was used to calculate Henry coefficients as well as the energies, entropies, and enthalpies for the different adsorption sites. Our simulations show that water has a surprisingly large affinity for the metal center in Cu−BTC compared to other that for molecules like carbon dioxide, nitrogen, oxygen, or hydrocarbons. This particular behavior could be further exploited for the separation of water from other compounds.
A matter of degree: Separation of di‐branched alkanes from their linear and mono‐branched isomers is important in producing high‐octane gasoline. Using computational techniques to screen a large ...variety of adsorbent materials (see scheme), ZIF‐77 emerges as the best adsorbent. It has the unique ability to fractionate isomer mixtures according to the degree of branching.
We use molecular simulations to analyze the preferential adsorption sites of molecules that differ in size, shape, and polarizability in Cu-BTC metal organic framework. The cage system of the ...framework can be exploited to enhance adsorption of small gases. We find that nonpolar molecules adsorb preferentially in the small tetrahedral cages, whereas alcohols and water molecules adsorb close to the copper atoms in one of the big cages. Blocking potentially enhances selective adsorption and separation and we therefore investigate how to block these cages in a practical manner. We propose to use ionic liquids for it and we find that the addition of these components reduces the adsorption of polar molecules near the open metal centers. For this reason, the presence of ionic liquids reduces the attack of the molecules of water to the metallic centers improving the framework stability.
We report a molecular simulation study aimed to ascertain the effect exerted in gas adsorption when room-temperature ionic liquids (RTILs) are added into the pores of the Cu-BTC metal-organic ...framework (MOF). Carbon dioxide, methane, nitrogen, and their mixtures are studied. We take into account the influence of the type of anion and the relative amount of RTILs used. It is observed that the presence of RTILs in the MOF pores enhances significantly CO2 adsorption at low pressures, whereas methane and nitrogen adsorption is unaffected.
In this work, we analyze the influence of small adsorbates on the vibrational spectra of Mg- and Zn-metal–organic framework MOF-74 by means of first-principles calculations. In particular, we ...consider the adsorption of four representative species of different interaction strengths: Ar, CO2, H2O, and NH3. Apart from a comprehensive characterization of the structural and energetic aspects of empty and loaded MOFs, we use a fully quantum ab initio approach to evaluate the Raman and IR activities of the normal modes, leading to the construction of the whole vibrational spectra. Under this approach, not only are we able to proceed with the complete assignment of the spectra in terms of the usual internal coordinates but also we can discern the most relevant vibrational fingerprints of the adsorbates and their impact on the whole MOF spectra. On the one hand, some of the typical vibrational modes of the small molecules are slightly shifted but still visible when adsorbed on the MOFs, especially those appearing at high wavenumbers where the empty MOFs lack IR/Raman signals. On the other hand, some bands arising from the organic ligands are affected by the presence of the absorbates, displaying non-negligible frequency shifts, in agreement with recent experiments. We find a strong correlation between all of these frequency shifts and the interaction strength of the adsorbate with the hosting framework. The findings presented in this work expand the capabilities of vibrational spectroscopy techniques to analyze porous materials and can be useful for the design of sensors and new devices based on MOF technology.
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