Controlling the Mobility of Ionic Liquids in the Nanopores of MOFs by Adjusting the Pore Size: From Conduction Collapse by Mutual Pore Blocking to Unhindered Ion Transport.

Ionic liquids (ILs) in nanoporous confinement are the core of many supercapacitors and batteries, where the mobility of the nanoconfined ILs is crucial. Here, by combining experiments based on impedance spectroscopy with molecular dynamics simulations, the mobility of a prototype IL in the nanopores of an isoreticular metal-organic framework (MOF)-series with different pore sizes is explored, where an external electric field is applied. It has been found that the conduction behavior changes tremendously depend on the pore size. For small-pore apertures, the IL cations and anions cannot pass the pore window simultaneously, causing the ions to mutually block the pores. This results in a strong concentration dependence of the ionic conduction, where the conduction drops by two orders of magnitude when filling the pores. For large-pore MOFs, the mutual hindrance of the ions in the pores is small, causing only a small concentration dependence. The cutoff between the large-pore and small-pore behavior is approximately the size of a cation-anion-dimer and increasing the pore diameter by only 0.2 nm changes the conduction behavior fundamentally. This study shows that the pore aperture size has a substantial effect on the mobility of ions in nanoporous confinement and has to be carefully optimized for realizing highly-mobile nanoconfined ILs.

Bunching and Immobilization of Ionic Liquids in Nanoporous Metal-Organic Framework.

Room-temperature ionic liquids (ILs) are a unique, novel class of designer solvents and materials with exclusive properties, attracting substantial attention in fields like energy storage and supercapacitors as well as in ion-based signal processing and electronics. For most applications, ILs need to be incorporated or embedded in solid materials like porous hosts. We investigate the dynamic structure of ILs embedded in well-defined pores of metal-organic frameworks (MOFs). The experimental data combined with molecular dynamics simulations unveil astonishing dynamic properties of the IL in the MOF nanoconfinement. At low IL loadings, the ions drift in the pores along the electric field, whereas at high IL loadings, collective field-induced interactions of the cations and anions lead to blocking the transport, thus suppressing the ionic mobility and tremendously decreasing the conductivity. The mutual pore blockage causes immobilized ions in the pores, resulting in a highly inhomogeneous IL density and bunched-up ions at the clogged pores. These results provide novel molecular-level insights into the dynamics of ILs in nanoconfinement, significantly enhancing the tunability of IL material properties.

All-atom modeling of methacrylate-based multi-modal chromatography resins for Langmuir constant prediction of peptides.

In downstream processing, the intricate nature of the interactions between biomolecules and adsorbent materials presents a significant challenge in the prediction of their binding and elution behaviors. This complexity is further heightened in multi-modal chromatography (MMC), which employs two distinct binding mechanisms. To gain a deeper understanding of the involved interactions, simulating the adsorption of biomolecules on resin surfaces is a focal point of ongoing research. However, previous studies often simplified the adsorbent surface, modeling it as a flat or slightly curved plane without including a realistic backbone structure. Here, we introduce and validate two novel workflows aimed at predicting peptide binding behaviors in MMC, specifically targeting methacrylate-based resins. Our first achievement was the development of an all-atom model of a commercial MMC resin surface, incorporating its polymethacrylic backbone. Furthermore, we established and tested a workflow for rapid calculations of binding free energies (ΔG) with 10 linear peptides as target molecules. These ΔG calculations were effectively used to predict Langmuir constants, achieving a high coefficient of determination (R²) of 0.96. In subsequent benchmarking tests, our model outperformed established, simpler resin surface models in terms of predictive capabilities.

Challenges and limits of mechanical stability in 3D direct laser writing.

Direct laser writing is an effective technique for fabrication of complex 3D polymer networks using ultrashort laser pulses. Practically, it remains a challenge to design and fabricate high performance materials with different functions that possess a combination of high strength, substantial ductility, and tailored functionality, in particular for small feature sizes. To date, it is difficult to obtain a time-resolved microscopic picture of the printing process in operando. To close this gap, we herewith present a molecular dynamics simulation approach to model direct laser writing and investigate the effect of writing condition and aspect ratio on the mechanical properties of the printed polymer network. We show that writing conditions provide a possibility to tune the mechanical properties and an optimum writing condition can be applied to fabricate structures with improved mechanical properties. We reveal that beyond the writing parameters, aspect ratio plays an important role to tune the stiffness of the printed structures.

Tough, Transparent, 3D-Printable, and Self-Healing Poly(ethylene glycol)-Gel (PEGgel).

Polymer gels, such as hydrogels, have been widely used in biomedical applications, flexible electronics, and soft machines. Polymer network design and its contribution to the performance of gels has been extensively studied. In this study, the critical influence of the solvent nature on the mechanical properties and performance of soft polymer gels is demonstrated. A polymer gel platform based on poly(ethylene glycol) (PEG) as solvent is reported (PEGgel). Compared to the corresponding hydrogel or ethylene glycol gel, the PEGgel with physically cross-linked poly(hydroxyethyl methacrylate-co-acrylic acid) demonstrates high stretchability and toughness, rapid self-healing, and long-term stability. Depending on the molecular weight and fraction of PEG, the tensile strength of the PEGgels varies from 0.22 to 41.3 MPa, fracture strain from 12% to 4336%, modulus from 0.08 to 352 MPa, and toughness from 2.89 to 56.23 MJ m-3 . Finally, rapid self-healing of the PEGgel is demonstrated and a self-healing pneumatic actuator is fabricated by 3D-printing. The enhanced mechanical properties of the PEGgel system may be extended to other polymer networks (both chemically and physically cross-linked). Such a simple 3D-printable, self-healing, and tough soft material holds promise for broad applications in wearable electronics, soft actuators and robotics.

Structural and Dynamic Insights into the Conduction of Lithium-Ionic-Liquid Mixtures in Nanoporous Metal-Organic Frameworks as Solid-State Electrolytes.

Metal-organic framework (MOF)-based separators in Li-ion batteries (LIBs) have the potential to improve the battery performance. The mobility and conduction of lithium and organic ionic liquids (ILs) in these materials acting as (quasi) solid-state electrolytes are crucial for the battery power output. Here, we investigate the mobility of a Li-based IL in MOF nanopores and unveil the details of the conduction mechanism by molecular dynamics (MD) simulations. A complex conductivity depending on the Li-IL loading and on the IL composition is observed. Most importantly, the presence of Li prevents the collapse of the conductivity at high IL loadings. The fully atomistic MD simulations including guest-guest and guest-host interactions elucidate the competing mechanisms: Li follows a Grotthuss-like conduction mechanism with large mobility. While at small pore fillings, the Li conduction is limited by the large distance between the anions facilitating the Grotthuss-like conduction; the conduction at high pore fillings is governed by field-induced concentration inhomogeneities. Because of the small MOF pore windows, which hinders the simultaneous passage of the large IL cations and anions in opposite directions, the IL shows field-induced MOF pore blocking and ion bunching. The regions of low anion concentration and high cation concentration represent barriers for Li, decreasing its mobility. In comparison to Li-free IL, the IL bunching effect is attenuated by the formation of charge-neutral Li-anion complexes, resulting in a tremendously increased conductivity at maximum pore filling. The exploitation of this mechanism may enhance the development of advanced batteries based on IL and nanoporous separators.