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This work integrates experiments and computational methods to quantify how the cis/trans ratio of the OSDA used in SSZ-39 synthesis impacts the crystallization kinetics, material properties, and final product composition. The crystallization kinetics increase by 30% when increasing the trans isomer content from 14% to 80%. Per prior work, in all cases based on the synthesis gel composition and product yield aluminum is the limiting reagent, and the absence of any amorphous material detected in the time resolved PXRD studies leads us to conclude that FAU dissolution is the rate limiting step in the formation of SSZ-39 in this synthesis protocol. The TGA and NMR results suggest that the trans isomer of OSDA is selectively incorporated into the product. The NMR binding studies, and corresponding DFT-based results show that the trans isomer binds to FAU more strongly than the cis isomer, providing one possible explanation for this enhancement in kinetics and preferential uptake of the trans isomer. The EDS analysis indicates that the Si/Al ratios are between 7.7 and 8.6 at low and high trans OSDA content, indicating zeolite composition is mildly sensitive to the trans isomer content. EDS results show this decrease in aluminum content leads to a corresponding decrease in sodium uptake. DFT-based calculations confirm OSDA–sodium interactions cannot explain any decrease in sodium uptake, reinforcing lower aluminum content as the cause of lower sodium uptake. Preliminary cobalt titration experiments show a surprisingly low cobalt uptake but also show a clear dependence of the cobalt uptake on the solution pH. 

Despite their widespread use, the mechanisms governing the synthesis of zeolite catalysts are still poorly understood. A notable example of this problem is the uncertainty surrounding the influence of synthesis conditions on the placement of Al atoms in the zeolite framework, which determines the active sites available for catalytic species. In this work, the role of the cis to trans isomer ratio of the OSDA N,N-dimethyl-3-5-dimethylpiperidinium on the energetics of 26 distinct Al pair distributions in SSZ-39 is examined both in the presence and absence of Na using density functional theory calculations. The initial orientation of the OSDA was found to have a significant impact on the final energies present, necessitating the screening of a large number of initial orientations with force field calculations and single point DFT calculations. Ground state energies were found to vary significantly with the ratio of cis to trans OSDAs with a Boltzmann distribution revealing the most likely Al pair distributions shift from sharing the same 8 membered rings to sharing the same double 6-membered rings to having no shared subunits as one increases the amount of cis OSDA present within the framework. The presence of Na was found to favor Al pair distributions where both Als occupied the same 6-membered ring. When an implicit solvent model was used to evaluate ground state energies the ideal Na sites shifted from 6-membered rings to empty SSZ-39 cages while OSDA positions and orientations remained largely the same. To provide insight on how kinetic factors may influence Al distributions, formation energies we calculated for connected double 6-membered rings. These formation energies revealed a preference for Al pairs to occupy the same 4-membered ring, which indicates kinetic and thermodynamic control may lead to different Al distributions in SSZ-39. 

A silver nanowire (AgNW) based conductor is a promising component for flexible and stretchable electronics. A wide range of flexible/stretchable devices using AgNW conductors has been demonstrated recently. High-resolution, high-throughput printing of AgNWs remains a critical challenge. Electrohydrodynamic (EHD) printing has been developed as a promising technique to print different materials on a variety of substrates with high resolution. Here, AgNW ink was developed for EHD printing. The printed features can be controlled by several parameters including AgNW concentration, ink viscosity, printing speed, stand-off distance, etc . With this method, AgNW patterns can be printed on a range of substrates, e.g. paper, polyethylene terephthalate (PET), glass, polydimethylsiloxane (PDMS), etc. First, AgNW samples on PDMS were characterized under bending and stretching. Then AgNW heaters and electrocardiogram (ECG) electrodes were fabricated to demonstrate the potential of this printing technique for AgNW-based flexible and stretchable devices. 

Subcritical hydrothermal liquefaction uses high temperatures (270-350°C) and high pressures (80-173 bar) to produce bio-crude oils that can be upgraded to liquid transportation fuels. In this study, two strains of Galdieria sulphuraria, an acidophilic, mixotrophic red microalgae, were cultivated on effluent from primary settling tanks at a municipal wastewater treatment plant. Samples were concentrated to 5 and 10 wt.% slurries after harvest and converted by hydrothermal liquefaction in a 1.8 L batch reactor. Reaction conditions included temperatures of 310, 330 and 350°C, and hold times of 5, 30 and 60 minutes. Yields and product properties were compared to those of hydrothermal liquefaction of Galdieria sulphuraria grown on media. Total oil yields were low (11-18 wt.%) and char yields were high (28-36 wt.%) compared to those from HTL of the algae grown on media (27-35 wt.% oil and 10-13 wt.% char), likely due to the higher ash content and lower lipid content of the algae grown on wastewater. The bio-crude oil, char, and aqueous phase samples were characterized to complete mass, energy and nutrient balances to characterize the tradeoffs in the algae growth and conversion systems for energy and nutrient recovery.