Synthesis of Nano/Microsized MIL-101Cr Through Combination of Microwave Heating and Emulsion Technology for Mixed-Matrix Membranes.

Nano/microsized MIL-101Cr was synthesized by microwave heating of emulsions for the use as a composite with Matrimid mixed-matrix membranes (MMM) to enhance the performance of a mixed-gas-separation. As an example, we chose CO2/CH4 separation. Although the incorporation of MIL-101Cr in MMMs is well-known, the impact of nanosized MIL-101Cr in MMMs is new and shows an improvement compared to microsized MIL-101Cr under the same conditions and mixed-gas permeation. In order to reproducibly obtain nanoMIL-101Cr microwave heating was supplemented by carrying out the reaction of chromium nitrate and 1,4-benzenedicarboxylic acid in heptane-in-water emulsions with the anionic surfactant sodium oleate as emulsifier. The use of this emulsion with the phase inversion temperature (PIT) method offered controlled nucleation and growth of nanoMIL-101 particles to an average size of <100 nm within 70 min offering high apparent BET surface areas (2,900 m2 g-1) and yields of 45%. Concerning the CO2/CH4 separation, the best result was obtained with 24 wt.% of nanoMIL-101Cr@Matrimid, leading to 32 Barrer in CO2 permeability compared to six Barrer for the neat Matrimid polymer membrane and 21 Barrer for the maximum possible 20 wt.% of microMIL-101Cr@Matrimid. The nanosized filler allowed reaching a higher loading where the permeability significantly increased above the predictions from Maxwell and free-fractional-volume modeling. These improvements for MMMs based on nanosized MIL-101Cr are promising for other gas separations.

Simple and High Yield Synthesis of Metal-Polymer Nanocomposites: The Role of Theta-Centrifugation as an Essential Purification Step.

Nanocomposites are an important materials class, which strives to foster synergistic effects from the intimate mixture of two vastly different materials. Inorganic nanoparticles decorated with polymer ligands, for instance, aim to combine the processing flexibility of polymers with the mechanical robustness of solid state materials. The fabrication and purification of such composite nanoparticles, however, still presents a synthetic challenge. Here, we present a simple synthesis of silver polystyrene nanocomposites with a controllable interparticle distance. The interparticle distance can be well-controlled with a few nanometer precision using polystyrene ligands with various molecular weights. The nanoparticle and polymer ligand synthesis yield both materials on gram scales. Consequently, the polymer nanocomposites can also be fabricated in such large amounts. Most importantly, we introduce Θ-centrifugation as a purification method, which is capable of purifying large nanocomposite batches in a reproducible manner. We employ a range of characterization methods to prove the successful purification procedure, such as transmission electron microscopy, thermogravimetric analysis, and dynamic light scattering. Our contribution will be of high interest for many groups working on nanocomposite materials, where the sample purification has been a challenge up to now.

Unusual and Superfast Temperature-Triggered Actuators.

A superfast actuator based on a bilayer fibrous mat shows folding/unfolding and the formation of 3D structures in a fraction of a second. The actuation is reversible for many cycles without losing its form and size, with unfolding at room temperature and folding above 35 °C. The system is promising for making 3D bioscaffolds, electrodes, and micro-/macroactuators.