Mark A. Snyder

Grain boundary defect elimination in a zeolite membrane by rapid thermal processing.

Optimizing Molecular Sieve Production Microporous membranes composed of aluminosilicate minerals are known as zeolites and are often called molecular sieves because of their ability to filter or separate small molecules. The separation performance is partly governed by the selectivity for one species over another, and this can be compromised by defects, which allow for easy diffusion pathways. To create the porosity, structure-directing agents are used, which need to be removed during a long thermal treatment that can generate defects. Choi et al. (p. 590) show that for the silicalite-1 system, a rapid thermal treatment significantly reduces the defect density, with corresponding improvement in the filtration of very similar species, such as xylene isomers. A reduction in the formation of defects in silicalite-1 zeolite membranes improves their isomer separation capabilities. Microporous molecular sieve catalysts and adsorbents discriminate molecules on the basis of size and shape. Interest in molecular sieve films stems from their potential for energy-efficient membrane separations. However, grain boundary defects, formed in response to stresses induced by heat treatment, compromise their selectivity by creating nonselective transport pathways for permeating molecules. We show that rapid thermal processing can improve the separation performance of thick columnar films of a certain zeolite (silicalite-1) by eliminating grain boundary defects, possibly by strengthening grain bonding at the grain boundaries. This methodology enables the preparation of silicalite-1 membranes with high separation performance for aromatic and linear versus branched hydrocarbon isomers and holds promise for realizing high-throughput and scalable production of these zeolite membranes with improved energy efficiency.

Direct, single-step synthesis of hierarchical zeolites without secondary templating

Hierarchical ZSM-5 was directly synthesized by controlling the nucleation, growth and template-free self-assembly of zeolite precursors formed in the initial stage of the zeolite crystallization process. The facile synthesis results in spherical particles primarily composed of a micro-mesoporous core of aggregated 30–50 nm MFI nanocrystals, and a thin crystalline shell. MFI nanocrystal assembly coupled with a possible dissolution–crystallization mechanism results in a template-free route to broadly distributed mesopores and, thereby, a ca. 25 nm diffusion length in a micrometer-sized particle. The materials exhibit enhanced mass transport and superior catalytic activity for bulky molecules.

Water transport through functionalized nanotubes with tunable hydrophobicity

Molecular dynamics simulations are used to study the occupancy and flow of water through nanotubes comprised of hydrophobic and hydrophilic atoms, which are arranged on a honeycomb lattice to mimic functionalized carbon nanotubes (CNTs). We consider single-file motion of TIP3P water through narrow channels of (6,6) CNTs with varying fractions (f) of hydrophilic atoms. Various arrangements of hydrophilic atoms are used to create heterogeneous nanotubes with separate hydrophobic/hydrophilic domains along the tube as well as random mixtures of the two types of atoms. The water occupancy inside the nanotube channel is found to vary nonlinearly as a function of f, and a small fraction of hydrophilic atoms (f ≈ 0.4) are sufficient to induce spontaneous and continuous filling of the nanotube. Interestingly, the average number of water molecules inside the channel and water flux through the nanotube are less sensitive to the specific arrangement of hydrophilic atoms than to the fraction, f. Two different regimes are observed for the water flux dependence on f - an approximately linear increase in flux as a function of f for f < 0.4, and almost no change in flux for higher f values, similar to the change in water occupancy. We are able to define an effective interaction strength between nanotube atoms and waters oxygen, based on a linear combination of interaction strengths between hydrophobic and hydrophilic nanotube atoms and water, that can quantitatively capture the observed behavior.

Geometric Model Describing the Banded Morphology of Particle Films Formed by Convective Assembly

Nanoparticle films coated on smooth substrates by convective assembly from dilute suspensions in dip-coating configuration are known to have discrete film morphologies. Specifically, the film morphology is characterized by alternating bands of densely packed particles and bands of bare substrate. Convective assembly is a frontal film-growth process that occurs at the three-phase contact line formed by the substrate, the suspension in which it is submersed, and the surrounding air. The bands are parallel to this contact line and can be either monolayered or multilayered. Monolayered bands result whenever the substrate is withdrawn from the suspension at a rate too high for particles to assemble into a continuous film. We report a new insight to the mechanism behind this banding phenomenon, namely, that inter-band spacing is strongly influenced by the constituent particle size. We therefore propose a geometric model relating the inter-band spacing to the particle size. By making banded films with systematically varied particle sizes (silica/zeolite, 20 to 500 nm), we are able to quantitatively validate our model. Furthermore, the model correctly predicts that multilayered banded films have higher inter-band spacings than monolayered banded films comprising the same particles.

A Review of Biorefinery Separations for Bioproduct Production via Thermocatalytic Processing

With technological advancement of thermocatalytic processes for valorizing renewable biomass carbon, development of effective separation technologies for selective recovery of bioproducts from complex reaction media and their purification becomes essential. The high thermal sensitivity of biomass intermediates and their low volatility and high reactivity, along with the use of dilute solutions, make the bioproducts separations energy intensive and expensive. Novel separation techniques, including solvent extraction in biphasic systems and reactive adsorption using zeolite and carbon sorbents, membranes, and chromatography, have been developed. In parallel with experimental efforts, multiscale simulations have been reported for predicting solvent selection and adsorption separation. We discuss various separations that are potentially valuable to future biorefineries and the factors controlling separation performance. Particular emphasis is given to current gaps and opportunities for future development.

Effect of molecular structure on fluid transport through carbon nanotubes

We perform molecular dynamics simulations to study the transport of geometrically modified water models through channels of carbon nanotube (CNT) membranes. We use two modifications to an existing water model (extended simple point charge SPC/E) as representative surrogates of molecular fluids: (1) bent model (model B) in which the HOH angle is varied while keeping the dipole moment constant by adjusting the OH bond length and (2) modified bent model (model MB) in which the HOH angle changes without any change in OH bond length thereby changing the dipole moment. Interestingly, we find that the fluid transport is a nonmonotonic function of the bond angle for both fluid models. This observed trend is not anticipated based on the fluid density as a function of the bond angle inside and outside of the nanotube channel. However, the average residence time of transmitted molecules through the channel provides an approximately inverse linear correlation with the observed flux, independent of the fluid model. Based on these correlations, we have developed an empirical design parameter connecting fluid transport through CNTs as a function of average occupancy (number of fluid molecules inside the nanotube) and the average residence time. Our results suggest that transport through carbon nanotubes can be sensitive to small changes in the structure of fluid molecules that can potentially be utilised for mixture separation.