Insights into water extraction and aggregation mechanisms of malonamide-alkane mixtures.

Structure at the nanoscale in the organic phase of liquid-liquid extraction systems is often tied to separation performance. However, the weak interactions that drive extractant assembly lead to poorly defined structures that are challenging to identify. Here, we investigate the mechanism of water extraction for a malonamide extractant commonly applied to f-element separations. We measure extractant concentration fluctuations in the organic phase with small angle X-ray scattering (SAXS) before and after contact with water at fine increments of extractant concentration, finding no qualitative changes upon water uptake that might suggest significant nanoscopic reorganization of the solution. The critical composition for maximum fluctuation intensity is consistent with small water-extractant adducts. The extractant concentration dependence of water extraction is consistent with a power law close to unity in the low concentration regime, suggesting the formation of 1 : 1 water-extractant adducts as the primary extraction mechanism at low concentration. At higher extractant concentrations, the power law slope increases slightly, which we find is consistent with activity effects modeled using Flory-Huggins theory without introduction of additional extractant-water species. Molecular dynamics simulations are consistent with these findings. The decrease in interfacial tension with increasing extractant concentration shows a narrow plateau region, but it is not correlated with any change in fluctuation or water extraction trends, further suggesting no supramolecular organization such as reverse micellization. This study suggests that water extraction in this system is particularly simple: it relies on a single mechanism at all extractant concentrations, and only slightly enhances the concentration fluctuations characteristic of the dry binary extractant/diluent mixture.

Critical fluctuations in liquid-liquid extraction organic phases controlled by extractant and diluent molecular structure.

Extractant aggregation in liquid-liquid extraction organic phases impacts extraction energetics and is related to the deleterious efficiency-limiting liquid-liquid phase transition known as third phase formation. Using small angle X-ray scattering, we find that structural heterogeneities across a wide range of compositions in binary mixtures of malonamide extractants and alkane diluents are well described by Ornstein-Zernike scattering. This suggests that structure in these simplified organic phases originates from the critical point associated with the liquid-liquid phase transition. To confirm this, we measure the temperature dependence of the organic phase structure, finding critical exponents consistent with the 3D Ising model. Molecular dynamics simulations were also consistent with this mechanism for extractant aggregation. Due to the absence of water or any other polar solutes required to form reverse-micellar-like nanostructures, these fluctuations are inherent to the binary extractant/diluent mixture. We also show how the molecular structure of the extractant and diluent modulate these critical concentration fluctuations by shifting the critical temperature: critical fluctuations are suppressed by increasing extractant alkyl tail lengths or decreasing diluent alkyl chain lengths. This is consistent with how extractant and diluent molecular structure are known to impact metal and acid loading capacity in many-component LLE organic phases, suggesting phase behavior of practical systems may be effectively studied in simplified organic phases. Overall, the explicit connection between molecular structure, aggregation and phase behavior demonstrated here will enable the design of more efficient separations processes.

Mechanistic Investigations into and Control of Anisotropic Metal-Organic Framework Growth.

The porphyrinic metal-organic framework, PCN-222, exhibits anisotropic growth behavior to form nanorods and microrods with aspect ratios 3 < x < 94. Control of microrod aspect ratios has been demonstrated through the identification of several factors that dictate crystal growth, particularly the concentrations of a ligand, a modulator, and an exogenous base. An increase in the local concentration of a deprotonated ligand, which is proportional to the nucleation rate, is associated with smaller crystals, while increased modulator concentration leads to longer microrods. Addition of a deprotonating agent not only contributes to higher aspect ratios but also results in an improvement to particle dispersity. Here, we report acid-base co-modulation methods with difluoroacetic acid and triethylamine to effectively tune PCN-222 aspect ratios. A series of mechanisms is identified for the growth of PCN-222: (1) ligand deprotonation, (2) nucleation, (3) oriented attachment, (4) Ostwald ripening, and (5) dissolution-recrystallization. Time trials of co-modulated samples revealed three separate ripening growth events, with each resulting in larger and more monodisperse crystals. With an understanding of these crystal growth factors and mechanisms, the highest aspect ratio, non-templated metal-organic frameworks were synthesized (94 ± 9).

Understanding the Mechanical Reinforcement of Metal-Organic Framework-Polymer Composites: The Effect of Aspect Ratio.

The aspect ratio (AR) of filler particles is one of the most critical determinants for the mechanical properties of particle-reinforced polymer composites. However, it has been challenging to solely study the effect of particle AR due to the difficulties of controlling AR without altering the physical and chemical properties of the particle. Herein, we synthesized PCN-222, a zirconium-based porphyrinic metal-organic framework (MOF) with preferential longitudinal growth as a series of particles with ARs increasing from 3.4 to 54. The synthetic MOF conditions allowed for the chemical properties of the particles to remain constant over the series. The particles were employed as reinforcers for poly(methyl methacrylate) (PMMA). MOF-polymer composite films were fabricated using doctor-blading techniques, which facilitated particle dispersion and alignment in the PMMA matrix, as revealed by optical microscopy and wide-angle X-ray diffraction. Mechanical measurements showed that both elastic and dynamic moduli increased with particle AR and particle concentrations but started to decrease as particle loading increased beyond 0.5 wt % (1.12 vol %). The data obtained at low particle loadings were fitted well with the Halpin-Tsai model. In contrast, the percolation model and the Cox model were unable to adequately fit the data, indicating the mechanical reinforcement in our system mainly originated from efficient load transfer between particles and the matrix in the particle orienting direction. Finally, we showed that the thermal stability of composite films increased with the addition of MOF particles because of the high thermal degradation temperature and restricted polymer chain mobility.

PCN-222 Metal-Organic Framework Nanoparticles with Tunable Pore Size for Nanocomposite Reverse Osmosis Membranes.

Nanorods of PCN-222, a large-pore, zirconium-based porphyrinic metal-organic framework (MOF), have been prepared through coordination modulation-controlled crystal growth through competing monodentate ligands known as modulators-for incorporation into reverse osmosis thin-film nanocomposite (TFN) membranes. Postsynthetic modification of the MOF node through binding of myristic acid (MA) altered channel dimensions and pore size distribution. The extent of MOF modification was characterized through Brunauer-Emmett-Teller gas sorption and 1H NMR following digestion of the particles. TFN membranes containing PCN-222 nanoparticles modified with varying levels of MA were fabricated via dispersion in the aqueous phase during interfacial polymerization, and the resulting flux and rejection performance of each membrane were evaluated. Increased water flux was observed with increasing MA content in the PCN-222 nanorods. Up to 95% increase in water flux was observed for a TFN containing 0.01 wt % loading of PCN-222 nanorods with a 10:1 MA to linker ratio, while maintaining high salt rejection. The flux change was attributed to tunable water transport through the nanorod pore structure and also through rapid water transport pathways at the nanorod-polymer interface.