H. Jeremy Cho

Characterization of Adsorption Enthalpy of Novel Water-Stable Zeolites and Metal-Organic Frameworks.

Water adsorption is becoming increasingly important for many applications including thermal energy storage, desalination, and water harvesting. To develop such applications, it is essential to understand both adsorbent-adsorbate and adsorbate-adsorbate interactions, and also the energy required for adsorption/desorption processes of porous material-adsorbate systems, such as zeolites and metal-organic frameworks (MOFs). In this study, we present a technique to characterize the enthalpy of adsorption/desorption of zeolites and MOF-801 with water as an adsorbate by conducting desorption experiments with conventional differential scanning calorimetry (DSC) and thermogravimetric analyzer (TGA). With this method, the enthalpies of adsorption of previously uncharacterized adsorbents were estimated as a function of both uptake and temperature. Our characterizations indicate that the adsorption enthalpies of type I zeolites can increase to greater than twice the latent heat whereas adsorption enthalpies of MOF-801 are nearly constant for a wide range of vapor uptakes.

Liquid Evaporation on Superhydrophobic and Superhydrophilic Nanostructured Surfaces

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Porosimetry and packing morphology of vertically aligned carbon nanotube arrays via impedance spectroscopy

Vertically aligned one-dimensional nanostructure arrays are promising in many applications such as electrochemical systems, solar cells, and electronics, taking advantage of high surface area per unit volume, nanometer length scale packing, and alignment leading to high conductivity. However, many devices need to optimize arrays for device performance by selecting an appropriate morphology. Developing a simple, non-invasive tool for understanding the role of pore volume distribution and interspacing would aid in the optimization of nanostructure morphologies in electrodes. In this work, we combined electrochemical impedance spectroscopy (EIS) with capacitance measurements and porous electrode theory to conduct in situ porosimetry of vertically-aligned carbon nanotubes (VA-CNTs) non-destructively. We utilized the EIS measurements with a pore size distribution model to quantify the average and dispersion of inter-CNT spacing (Γ), stochastically, in carpets that were mechanically densified from 1.7 × 1010 tubes/cm2 to 4.5 × 1011 tubes/cm2. Our analysis predicts that the inter-CNT spacing ranges from over 100 ± 50 nm in sparse carpets to sub 10 ± 5 nm in packed carpets. Our results suggest that waviness of CNTs leads to variations in the inter-CNT spacing, which can be significant in sparse carpets. This methodology can be used to predict the performance of many nanostructured devices, including supercapacitors, batteries, solar cells, and semiconductor electronics.

Understanding Enhanced Boiling With Triton X Surfactants

Heat transfer performance in pool boiling is largely dictated by bubble growth, departure, and number of nucleation sites. It is a well known phenomenon that adding surfactants can lower the liquid-vapor surface tension and increase the bubble departure frequency, thereby enhancing heat transfer. In addition to faster departure rates, surfactants are observed to dramatically increase the number of nucleation sites, which cannot be explained by simple surface tension arguments. Furthermore, it is not well understood which surfactant properties such as chemical composition and molecular structure affect boiling most significantly. From our experiments using Triton X-100 and Triton X-114 nonionic surfactants, we attribute boiling enhancement mainly to adsorption to the solid-liquid interface. Using the Mikic-Rohsenow model for boiling, a simple linear adsorption model, and the Cassie-Baxter description for contact angle, we developed a model that shows agreement with experimental results. This work offers some insights on how to predict boiling enhancement based on surfactant chemistry alone, which may aid in choosing optimal surfactants for boiling in the future.© 2013 ASME

Predicting Surface Tensions of Surfactant Solutions from Statistical Mechanics

The importance of surfactants to various industries necessitates a predictive understanding of their surface tension and adsorption behavior in terms of molecular characteristics. Previous models are highly empirical, require fitting parameters, and have limited applicability at various temperatures. Here, we provide a surface tension model based on statistical mechanics that (1) is thermodynamically consistent, (2) provides a higher predictive power, wherein surface tension can be calculated for any tail length, concentration, and temperature from molecular parameters, and (3) provides a physical understanding of the important molecular interactions at play. This model is applicable to both nonionic and ionic surfactants, where the effects of the electric double layer have been taken into account in the latter case. For nonionic surfactants, we were able to extend our model to predict dynamic surface tension as well. We have validated our model with tensiometry experiments for various surfactants, concentrations, and temperatures. In addition, we have validated our model with a diverse set of literature data, wherein agreement within a few mN M-1 and a correct prediction of phase change behavior is shown. The model could enable a more informed design of surfactant systems and serve as the theoretical basis for theory on more complex surfactant systems such as mixtures.

Characterization of Lipid Membrane Properties for Tunable Electroporation

Lipid bilayers form nanopores on the application of an electric field. This process of electroporation can be utilized in different applications ranging from targeted drug delivery in cells to nano-gating membrane for engineering applications. However, the ease of electroporation is dependent on the surface energy of the lipid layers and thus directly related to the packing structure of the lipid molecules. 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) lipid monolayers were deposited on a mica substrate using the Langmuir-Blodgett (LB) technique at different packing densities and analyzed using atomic force microscopy (AFM). The wetting behavior of these monolayers was investigated by contact angle measurement and molecular dynamics simulations. It was found that an equilibrium packing density of liquid-condensed (LC) phase DPPC likely exists and that water molecules can penetrate the monolayer displacing the lipid molecules. The surface tension of the monolayer in air and water was obtained along with its breakthrough force.© 2012 ASME

Wetting characteristics of a phospholipid membrane using molecular dynamics simulation

Phospholipid molecules form bilayers in water due to their hydrophilic heads and hydrophobic tails. The electroporation of lipid bilayers (cell membranes) is a phenomenon where membranes are permeabilized by the application of electric fields. At some critical voltage, a dramatic increase in conductivity across the membranes is observed. This phenomenon is widely used in DNA and RNA transfer as well as targeted drug delivery systems. However, the membrane ruptures with a continuous increase in voltage where interaction between lipid and water molecules is an important factor in electroporation behavior. This study characterizes the wettability, of both the head and tail groups of lipid molecules, by calculating the contact angle of a water droplet on a planar phospholipid monolayer using molecular dynamics simulations. The water droplet completely spreads on the hydrophilic heads of the lipid, while forming an average contact angle of 136.05° on the hydrophobic tails. An analysis using the Young’s equation suggests that a difference in free energy of 116 mJ/m2 contributes to the overall energy barrier for water penetration across the lipid monolayer. We aim to control this permeabilization phenomenon to achieve water desalination.Copyright