We report the electrochemical reduction of CO2 at copper foams with hierarchical porosity. We show that both the distribution of products formed from this reaction and their faradaic efficiencies differ significantly from those obtained at smooth electropolished copper electrodes. We attribute these differences to be due to high surface roughness, hierarchical porosity, and confinement of reactive species. We provide preliminary evidence in support of these claims.

This article reports a direct chemical pathway for antioxidant deactivation on the surfaces of carbon nanomaterials. In the absence of cells, carbon nanotubes are shown to deplete the key physiological antioxidant glutathione (GSH) in a reaction involving dissolved dioxygen that yields the oxidized dimer, GSSG, as the primary product. In both chemical and electrochemical experiments, oxygen is only consumed at a significant steady-state rate in the presence of both nanotubes and GSH. GSH deactivation occurs for single- and multi-walled nanotubes, graphene oxide, nanohorns, and carbon black at varying rates that are characteristic of the material. The GSH depletion rates can be partially unified by surface area normalization, are accelerated by nitrogen doping, and suppressed by defect annealing or addition of proteins or surfactants. We propose that dioxygen reacts with active sites on graphenic carbon surfaces to produce surface-bound oxygen intermediates that react heterogeneously with glutathione to restore the carbon surface and complete a catalytic cycle. The direct catalytic reaction between nanomaterial surfaces and antioxidants may contribute to oxidative stress pathways in nanotoxicity, and the dependence on surface area and structural defects suggest strategies for safe material design.

Viologens, either as anions in solution or as pendant substituents to pyrrole, were incorporated as dopants to electrodeposited films of polypyrrole. The resulting polymer films exhibited redox activity at -0.5 V vs Ag/AgCl. The film consisting of polypyrrole with pendant viologens exhibited the best charge-discharge behavior with a maximum capacity of 55 mAh/g at a discharge current of 0.25 mA/cm(2). An anode consisting of polypyrrole (pPy) doped with viologen (V) was coupled to a cathode consisting of pPy doped with 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) to yield a polymer-based battery with a cell electromotive force (emf) of 1.0 V, maximum capacity of 16 mAh/g, and energy density of 15 Wh/kg.

In this article, for the first time, in situ and real-time experimental observations of changes in solid/liquid (s/l) interface shape during interactions with a particle or void are reported for metallic systems. Real-time interface shape evolution for both stationary and growing interfaces was observed by use of a state-of-the-art X-ray transmission microscope. Localized interfacial perturbations were studied as a function of the particle or void diameter, the distance between the s/l interface and the particle or void, and the thermal conductivity ratio between the matrix and the particle or void. In particular, the sensitivity of interfacial perturbation to the thermal conductivity ratio is critically analyzed. Analytical predictions of interface shape are compared to the real-time, in situ experimental data. A good agreement between the experimentally observed and predicted interface shapes was found for stationary interfaces. Based on the differences in experimental observations, between a moving and a stationary interface, an alternate hypothesis is suggested to explain the observed kinetics of particle engulfment by a growing interface.

We investigate tin (Sn) and tin oxide (SnO 2 ) nanoparticle catalysts deposited on gas diffusion layers for the electrochemical reduction of carbon dioxide (CO 2 ) to formate. The performance and durability of these electrodes was evaluated in a gas-fed electrolysis cell with a flowing liquid electrolyte stream and an integrated reference electrode. The SnO 2 electrodes achieved peak current densities of 385 ± 19 mA cm -2 while the Sn electrodes achieved peak current densities of 214 ± 6 mA cm -2 , both at a formate selectivity > 70%. The associated peak formate production rates of 7.4 ± 0.6 mmol m -2 s -1 (Sn) and 14.9 ± 0.8 mmol m -2 s -1 (SnO 2 ) were demonstrated for a 1 h electrolysis and compare favorably to prior literature. Post-test analyses reveal chemical and physical changes to both cathodes during electrolysis including oxide reduction at applied potentials less than -0.6 V vs. RHE, nanoparticle aggregation, and catalyst layer erosion. Understanding and mitigating these decay processes is key to extending electrode lifetime without sacrificing formate generation rates or process efficiency.

This study presents a new approach to the formulation of functional nanofluids with high solid loading and low viscosity while retaining the surface activity of nanoparticles, in particular, their electrochemical response. The proposed methodology can be applied to a variety of functional nanomaterials and enables exploration of nanofluids as a medium for industrial applications beyond heat transfer fluids, taking advantage of both liquid behavior and functionality of dispersed nanoparticles. The highest particle concentration achievable with pristine 25 nm titania (TiO2) nanoparticles in aqueous electrolytes (pH 11) is 20 wt %, which is limited by particle aggregation and high viscosity. We have developed a scalable one-step surface modification procedure for functionalizing those TiO2 nanoparticles with a monolayer coverage of propyl sulfonate groups, which provides steric and charge-based separation of particles in suspension. Stable nanofluids with TiO2 loadings up to 50 wt % and low viscosity are successfully prepared from surface-modified TiO2 nanoparticles in the same electrolytes. Viscosity and thermal conductivity of the resulting nanofluids are evaluated and compared to nanofluids prepared from pristine nanoparticles. Furthermore, it is demonstrated that the surface-modified titania nanoparticles retain more than 78% of their electrochemical response as compared to that of the pristine material. Potential applications of the proposed nanofluids include, but are not limited to, electrochemical energy storage and catalysis, including photo- and electrocatalysis.

Results of the directional solidification (DS) experiments on particle engulfment and pushing by solidifying interfaces (PEP), conducted on the space shuttle Columbia during the Life and Microgravity Science (LMS) Mission, are reported. Two pure aluminum (99.999 pct) 9 mm cylindrical rods, loaded with about 2 vol pct 500-m-diameter zirconia particles, were melted and resolidified in the microgravity (g) environment of the shuttle. One sample was processed at a stepwise increased solidification velocity and the other at a stepwise decreased velocity. It was found that a pushing/engulfment transition (PET) occurred in the velocity range of 0.5 to 1 m/s. This is smaller than the ground PET velocity of 1.9 to 2.4 m/s. This demonstrates that natural convection increases the critical velocity. A previously proposed analytical model for PEP was further developed. A major effort to identify and produce data for the surface energy of various interfaces required for calculation was undertaken. The predicted critical velocity for PET was 0.775 m/s.

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