Design of Mixed-Matrix MOF Membranes with Asymmetric Filler Density and Intrinsic MOF/Polymer Compatibility for Enhanced Molecular Sieving.

The separation of high-value-added chemicals from organic solvents is important for many industries. Membrane-based nanofiltration offers a more energy-efficient separation than the conventional thermal processes. Conceivably, mixed-matrix membranes (MMMs), encompassing metal-organic frameworks (MOFs) as fillers, are poised to promote selective separation via molecular sieving, synergistically combining polymers flexibility and fine-tuned porosity of MOFs. Nevertheless, conventional direct mixing of MOFs with polymer solutions results in underutilization of the MOF fillers owing to their uniform cross-sectional distribution. Therefore, in this work, a multizoning technique is proposed to produce MMMs with an asymmetric-filler density, in which the MOF fillers are distributed only on the surface of the membrane, and a seamless interface at the nanoscale. The design strategy demonstrates five times higher MOF surface coverage, which results in a solvent permeance five times higher than that of conventional MMMs while maintaining high selectivity. Practically, MOFs are paired with polymers of similar chemical nature to enhance their adhesion without the need for surface modification. The approach offers permanently accessible MOF porosity, which translates to effective molecular sieving, as exemplified by the polybenzimidazole and Zr-BI-fcu-MOF system. The findings pave the way for the development of composite materials with a seamless interface.

Mass effects for thermodiffusion in dilute aqueous solutions.

Thermodiffusion is the phenomenon by which molecules in a mixture present concentration gradients in response to an imposed temperature gradient. Despite decades of investigations, this effect remains poorly understood at a molecular level. A common, phenomenological approach is to individuate the molecular factors that influence the Soret coefficient, the parameter that quantifies the resulting concentration-gradient. Experimental studies, often performed on organic mixtures, as well as simulations of model particle systems have evidenced that the difference in masses between the mixture components has an important effect on the amplitude of the Soret coefficient. Here, we use molecular dynamics simulations of a thermophoretic setting to investigate the mass dependence of the Soret coefficient in dilute aqueous solutions. An advantage of simulation approaches is that they are not limited in the range of explored molecular masses, which is often limited to isotopic substitutions in the experiments. Our simulations reveal that the mass dependence of the Soret coefficient in these solutions is in agreement with previous experimental and simulation work on molecular-size systems. In particular, it is sensitive to the relative mass difference between the solute and the solvent, but not to their absolute mass. Adjusting the mass of the solvent and of the solute can turn a thermophobic solution into a thermophilic one, where solute accumulation is reversed. This demonstrates that the mass effect can indeed compensate for the other contributions to the Soret coefficient. Finally, we find that changing the molecular moments of inertia has a much more limited impact as compared to a change in the total molecular mass.

In silico all-atom approach to thermodiffusion in dilute aqueous solutions.

Thermodiffusion (or thermophoresis) is the phenomenon by which the spatial distributions of constituents of liquid or gas phases become inhomogeneous in response to a temperature gradient. It has been evidenced in a variety of systems and has many practical applications as well as implications in the context of the origins of life. A complete molecular picture of thermophoresis is still missing, and phenomenological approaches are often employed to account for the experimental observations. In particular, the amplitude of the resulting concentration-gradients (quantified by the Soret coefficient) depends on many factors that are not straightforwardly rationalized. All-atom molecular dynamics simulations appear as an exquisite tool to shed light on the molecular origins for this phenomenon in molecular systems, but the practical implementation of thermophoretic settings in silico poses significant challenges. Here, we propose a robust approach to tackle thermophoresis in dilute realistic solutions at the molecular level. We rely on a recent enhanced heat-exchange algorithm to generate temperature-gradients. We carefully assess the convergence of thermophoretic simulations in dilute aqueous solutions. We show that simulations typically need to be propagated on long timescales (hundreds of nanoseconds). We find that the magnitude of the temperature gradient and the box sizes have little effect on the measured Soret coefficients. Practical guidelines are derived from such observations. Provided with this reliable setup, we discuss the results of thermophoretic simulations on several examples of molecular, neutral solutes, which we find in very good agreement with experimental measurements regarding the concentration-, mass-, and temperature-dependence of the Soret coefficient.

Distributed Gaussian orbitals for the description of electrons in an external potential.

In this work, we demonstrate the viability of using distributed Gaussian orbitals as a basis set for the calculation of the properties of electrons subjected to an external potential. We validate our method by studying one-electron systems for which we can compare to exact analytical results. We highlight numerical aspects that require particular care when using a distributedGaussian basis set. In particular, we discuss the optimal choice for the distance between two neighboring Gaussian orbitals. Finally, we show how our approach can be applied to many-electron problems.

Signatures of Wigner localization in one-dimensional systems.

We propose a simple and efficient approach to study Wigner localization in one-dimensional systems using ab initio theory. In particular, we propose a suitable basis for the study of localization which consists of equally spaced overlapping gaussians. We illustrate our approach with full-configuration interaction which yields exact results for a given basis set. With our approach, we were able to study up to 8 electrons with full-configuration interaction. Finally, we propose the total-position spread tensor and the total electron entropy as convenient quantities to obtain signatures of Wigner localization.