Nidia C. Gallego

Carbon foams for thermal management

A unique process for the fabrication of high-thermal-conductivity carbon foam was developed at Oak Ridge National Laboratory (ORNL). This process does not require the traditional blowing and stabilization steps and therefore is less costly. The resulting foam can have density values of between 0.2 and 0.6 g/cc and can develop a bulk thermal conductivity of between 40 and 180 W/m K. Because of its low density, its high thermal conductivity, its relatively high surface area, and its open-celled structure, the ORNL carbon foam is an ideal material for thermal management applications. Initial studies have shown the overall heat transfer coefficients of carbon foam-based heat sinks to be up to two orders of magnitude greater than those of conventional heat sinks.

Lab-in-a-Shell: Encapsulating Metal Clusters for Size Sieving Catalysis

Here we describe a lab-in-a-shell strategy for the preparation of multifunctional core-shell nanospheres consisting of a core of metal clusters and an outer microporous silica shell. Various metal clusters (e.g., Pd and Pt) were encapsulated and confined in the void space mediated by the entrapped polymer dots inside hollow silica nanospheres acting first as complexing agent for metal ions and additionally as encapsulator for clusters, limiting growth and suppressing the sintering. The Pd clusters encapsulated in hybrid core-shell structures exhibit exceptional size-selective catalysis in allylic oxidations of substrates with the same reactive site but different molecular size (cyclohexene ∼0.5 nm, cholesteryl acetate ∼1.91 nm). The solvent-free aerobic oxidation of diverse hydrocarbons and alcohols was further carried out to illustrate the benefits of such an architecture in catalysis. High activity, outstanding thermal stability and good recyclability were observed over the core-shell nanocatalyst.

Topological Defects: Origin of Nanopores and Enhanced Adsorption Performance in Nanoporous Carbon

A scanning transmission electron microscopy investigation of two nanoporous carbon materials, wood-based ultramicroporous carbon and poly(furfuryl alcohol)-derived carbon, is reported. Atomic-resolution images demonstrate they comprise isotropic, three-dimensional networks of wrinkled one-atom-thick graphene sheets. In each graphene plane, nonhexagonal defects are frequently observed as connected five- and seven-atom rings. Atomic-level modeling shows that these topological defects induce localized rippling of graphene sheets, which interferes with their graphitic stacking and induces nanopores that lead to enhanced adsorption of H(2) molecules. The poly(furfuryl alcohol)-derived carbon contains larger regions of stacked layers, and shows significantly smaller surface area and pore volume than the ultramicroporous carbon.

Crown ethers in graphene

Crown ethers are at their most basic level rings constructed of oxygen atoms linked by two- or three-carbon chains. They have attracted attention for their ability to selectively incorporate various atoms or molecules within the cavity formed by the ring. However, crown ethers are typically highly flexible, frustrating efforts to rigidify them for many uses that demand higher binding affinity and selectivity. Here we present atomic-resolution images of the same basic structures of the original crown ethers embedded in graphene. This arrangement constrains the crown ethers to be rigid and planar. First-principles calculations show that the close similarity of the structures should also extend to their selectivity towards specific metal cations. Crown ethers in graphene offer a simple environment that can be systematically tested and modelled. Thus, we expect that our finding will introduce a new wave of investigations and applications of chemically functionalized graphene.

Hydrogen confinement in carbon nanopores: extreme densification at ambient temperature.

In-situ small-angle neutron scattering studies of H(2) confined in small pores of polyfurfuryl alcohol-derived activated carbon at room temperature have provided for the first time its phase behavior in equilibrium with external H(2) at pressures up to 200 bar. The data were used to evaluate the density of the adsorbed fluid, which appears to be a function of both pore size and pressure and is comparable to the density of liquid H(2) in narrow nanopores at ∼200 bar. The surface-molecule interactions responsible for densification of H(2) within the pores create internal pressures that exceed the external gas pressure by a factor of up to ∼50, confirming the benefits of adsorptive storage over compressive storage. These results can be used to guide the development of new carbon adsorbents tailored for maximum H(2) storage capacities at near-ambient temperatures.

Forced Convection Heat Transfer and Hydraulic Losses in Graphitic Foam

Experiments and computations are presented to quantify the convective heat transfer and the hydraulic loss that is obtained by forcing water through blocks of graphitic foam (GF) heated from one side. Experiments have been conducted in a small-scale water tunnel instrumented to measure the pressure drop and the temperature rise of water passing through the foam and the base temperature and heat flux into the foam block. The experimental data were then used to calibrate a thermal non-equilibrium finite-volume model to facilitate comparisons between GF and aluminum foam. Comparisons of the pressure drop indicate that both normal and compressed aluminum foams are significantly more permeable than GF. Results of the heat transfer indicate that the maximum possible heat dissipation from a given surface is reached using very thin layers of aluminum foam due to the inability of the foam to entrain heat into its internal structure. In contrast, graphitic foam is able to entrain heat deep into the foam structure due to its high extended surface efficiency and thus much more heat can be transferred from a given surface area. The higher extended surface efficiency is mainly due to the combination of moderate porosity and higher solid-phase conductivity.

Thermal Treatment Effects on Charge Storage Performance of Graphene-Based Materials for Supercapacitors

Graphene materials were synthesized by reduction of exfoliated graphite oxide and then thermally treated in nitrogen to improve the surface area and their electrochemical performance as electrical double-layer capacitor electrodes. The structural and surface properties of the prepared reduced graphite oxide (RGO) were investigated using atomic force microscopy, scanning electron microscopy, Raman spectra, X-ray diffraction pattern analysis, and nitrogen adsorption/desorption studies. RGO forms a continuous network of crumpled sheets, which consist of large amounts of few-layer and single-layer graphenes. Electrochemical studies were conducted by cyclic voltammetry, impedance spectroscopy, and galvanostatic charge-discharge measurements. The modified RGO materials showed enhanced electrochemical performance, with maximum specific capacitance of 96 F/g, energy density of 12.8 Wh/kg, and power density of 160 kW/kg. These results demonstrate that thermal treatment of RGO at selected conditions is a convenient and efficient method for improving its specific capacitance, energy, and power density.

Characterization of Porous Carbon Foam as a Material for Compact Recuperators

Experiments are presented to quantify the convective heat transfer and hydrodynamic loss that is obtained by forcing water through blocks of porous carbon foam (PCF) heated from one side. The experiments were conducted in a small-scale water tunnel instrumented to measure the pressure drop and temperature rise of the water passing through the blocks and the base temperature and heat flux into the foam block. In comparison to similar porosity aluminum foam, the present results indicate that the pressure drop across the porous carbon foam is higher due to the large hydrodynamic loss associated with the cell windows connecting the pores, but the heat transfer performance suggests that there may be a significant advantage to using PCF over aluminum foam for extended surface convection elements in recuperators and electronic cooling devices.

Modern approaches to studying gas adsorption in nanoporous carbons

Conventional approaches to understanding the gas adsorption capacity of nanoporous carbons have emphasized the relationship with the effective surface area, but more recent work has demonstrated the importance of local structures and pore-size-dependent adsorption. These developments provide new insights into local structures in nanoporous carbon and their effect on gas adsorption and uptake characteristics. Experiments and theory show that appropriately tuned pores can strongly enhance local adsorption, and that pore sizes can be used to tune adsorption characteristics. In the case of H2 adsorbed on nanostructured carbon, quasielastic and inelastic neutron scattering probes demonstrate novel quantum effects in the motion of adsorbed molecules.

A study of poplar organosolv lignin after melt rheology treatment as carbon fiber precursors

Lignins from various poplar genotypes were isolated by using organosolv fractionation and subjected to rheological treatment at various temperatures. Physicochemical characterization of the lignin variants shows a broad distribution of glass transition temperatures, melt viscosity, and pyrolysis char residues. Rheological treatment at 170 °C induces lignin repolymerization accompanied with an increase in condensed linkages, molecular weights, and viscosities. In contrast, rheology testing at 190 °C results in the decrease in lignin aliphatic and phenolic hydroxyl groups, β-O-aryl ether linkages, molecular weights, and viscosity values. Lignin under air cooling generates more oxygenated and condensed compounds, but lower amounts of ether linkages than lignin cooled under nitrogen. Lignin with a lower syringyl/guaiacyl ratio tends to form more cross-linkages along with higher viscosity values, higher molecular weight and larger amounts of condensed bonds.