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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 1,621 records · Page 90
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Vapor Synthesis and Thermal Modification of Supportless Platinum–Ruthenium Nanotubes and Application as Methanol Electrooxidation Catalysts

Metallic, mixed-phase, and alloyed bimetallic Pt-Ru nanotubes were synthesized by a novel route based on the sublimation of metal acetylacetonate precursors and their subsequent vapor deposition within anodic alumina templates. Nanotube architectures were tuned by thermal annealing treatments. As-synthesized nanotubes are composed of nanoparticulate, metallic platinum and hydrous ruthenium oxide whose respective thicknesses depend on the sample chemical composition. The Pt-decorated, hydrous Ru oxide nanotubes may be thermally annealed to promote a series of chemical and physical changes to the nanotube structures including alloy formation, crystallite growth and morphological evolution. Annealed Pt-Ru alloy nanotubes and their as-synthesized analogs demonstrate relatively high specific activities for the oxidation of methanol. As-synthesized, mixed-phase Pt-Ru nanotubes (0.39 mA/cm2) and metallic alloyed Pt64Ru36NTs (0.33 mA/cm2) have considerably higher area-normalized activities than PtRu black (0.22 mA/cm2) at 0.65 V vs. RHE.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Effect of Surface Modification and Macrophage Phenotype on Particle Internalization

Material properties play a key role in the cellular internalization of polymeric particles. In the present study, we have investigated the effects of material characteristics such as water contact angle, zeta potential, melting temperature, and alternative activation of complement on particle internalization for pro-inflammatory, pro-angiogenic, and naïve macrophages by using biopolymers (~600 nm), functionalized with 13 different molecules. Understanding how material parameters influence particle internalization for different macrophage phenotypes is important for targeted delivery to specific cell populations. Here, we demonstrate that material parameters affect the alternative pathway of complement activation as well as particle internalization for different macrophage phenotypes. Here, we show that the quantitative structure–activity relationship method (QSAR) previously used to predict physiochemical properties of materials can be applied to targeting different macrophage phenotypes. These findings demonstrated that targeted drug delivery to macrophages could be achieved by exploiting material parameters.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Enhanced Fe2O3 Reducibility via Surface Modification with Pd: Characterizing the Synergy within Pd/Fe Catalysts for Hydrodeoxygenation Reactions

The synergistic catalysis in the hydrodeoxygenation of phenolic compounds over a Pd/Fe bimetallic surface has been well established. However, the nature of this synergy is still in part a mystery. In this work, we used a combined experimental and theoretical approach to understand a potential function of the surface Pd in the reduction of Pd/Fe2O3. This function of Pd was investigated via the comparison of the reduction properties as well as other physicochemical properties of samples synthesized by the reduction of Fe2O3 nanoparticles with and without surface Pd. Temperature-programmed reduction studies demonstrated the remarkable facilitation of reduction by addition of Pd, evidenced by a 150 degrees C shift toward lower temperature of the reduction peak of Fe3+. From X-ray photoelectron spectroscopy and theoretical calculation results, the interaction between Pd and the Fe2O3 surface occurs through the exchange of electrons with both the surface Fe and O atoms. This bonding between the Pd and surface oxide elements causes the Pd to partially donate electrons to the oxide surface, making the surface electrons more delocalized. This electron delocalization stabilizes the reduced oxide surfaces, as suggested by the TPR results and theoretical prediction. Therefore, the stabilization of the reduced Fe surface as well as the facilitated water formation by introduction of Pd is expected to significantly contribute to the Pd-Fe synergy in hydrodeoxygenation catalysis.

bimetallic catalysts↗
DOE OSTI2013

Modifications of Carbonate Fracture Hydrodynamic Properties by CO 2 -Acidified Brine Flow

Acidic reactive flow in fractures is relevant in subsurface activities such as CO{sub 2} geological storage and hydraulic fracturing. Understanding reaction-induced changes in fracture hydrodynamic properties is essential for predicting subsurface flows such as leakage, injectability, and fluid production. In this study, x-ray computed tomography scans of a fractured carbonate caprock were used to create three dimensional reconstructions of the fracture before and after reaction with CO{sub 2}-acidified brine (Ellis et al., 2011, Greenhouse Gases: Sci. Technol., 1:248-260). As expected, mechanical apertures were found to increase substantially, doubling and even tripling in some places. However, the surface geometry evolved in complex ways including ‘comb-tooth’ structures created from preferential dissolution of calcite in transverse sedimentary bands, and the creation of degraded zones, i.e. porous calcite-depleted areas on reacted fracture surfaces. These geometric alterations resulted in increased fracture roughness, as measured by surface Z{sub 2} parameters and fractal dimensions D{sub f}. Computational fluid dynamics (CFD) simulations were conducted to quantify the changes in hydraulic aperture, fracture transmissivity and permeability. The results show that the effective hydraulic apertures are smaller than the mechanical apertures, and the changes in hydraulic apertures are nonlinear. Overestimation of flow rate by a factor of two or more would be introduced if fracture hydrodynamic properties were based on mechanical apertures, or if hydraulic aperture is assumed to change proportionally with mechanical aperture. The differences can be attributed, in part, to the increase in roughness after reaction, and is likely affected by contiguous transverse sedimentary features. Hydraulic apertures estimated by the 1D statistical model and 2D local cubic law (LCL) model are consistently larger than those calculated from the CFD simulations. In addition, a novel ternary segmentation method was devised to handle the degraded zones, allowing for a bounding analysis of the effects on hydraulic properties. We found that the degraded zones account for less than 15% of the fracture volume, but cover 70% to 80% of the fracture surface. When the degraded zones are treated as part of the fracture, the fracture transmissivities are two to four times larger because the fracture surfaces after reaction are not as rough as they would be if one considers the degraded zone as part of the rock. Therefore, while degraded zones created during geochemical reactions may not significantly increase mechanical aperture, this type of feature cannot be ignored and should be treated with prudence when predicting fracture hydrodynamic properties.

roughness↗
DOE OSTI2021

Increasing Iridium Oxide Activity for the Oxygen Evolution Reaction with Hafnium Modification

Synthesis and implementation of highly active, stable, and affordable electrocatalysts for the oxygen evolution reaction (OER) is a major challenge in developing energy efficient and economically viable energy conversion devices such as electrolyzers, rechargeable metal-air batteries, and regenerative fuel cells. The current benchmark electrocatalyst for OER is based on iridium oxide (IrO x ) due to its superior performance and excellent stability. However, large scale applications using IrO x are impractical due to its low abundance and high cost. In this work, we report a highly active hafnium-modified iridium oxide (IrHf x O y ) electrocatalyst for OER. The IrHf x O y electrocatalyst demonstrated ten times higher activity in alkaline conditions (pH = 11) and four times higher activity in acid conditions (pH = 1) than a IrO x electrocatalyst. The highest intrinsic mass activity of the IrHf x O y catalyst in acid conditions was calculated as 6950 A gIrO x -1 at an overpotential (η) of 0.3 V. Combined studies utilizing operando surface enhanced Raman spectroscopy (SERS) and DFT calculations revealed that the active sites for OER are the Ir-O species for both IrO x and IrHf x O y catalysts. The presence of Hf sites leads to more negative charge states on nearby O sites, and shortening the bond lengths of Ir-O, and lowering free energies for OER intermediates to accelerate the OER process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Chemical Modifications of Ag Catalyst Surfaces with Imidazolium Ionomers Modulate H 2 Evolution Rates during Electrochemical CO 2 Reduction

Bridging polymer design with catalyst surface science is a promising direction for tuning and optimizing electrochemical reactors that could impact long-term goals in energy and sustainability. Particularly, the interaction between inorganic catalyst surfaces and organic-based ionomers provides an avenue to both steer reaction selectivity and promote activity. In this work, we studied the role of imidazolium-based ionomers for electrocatalytic CO 2 reduction to CO (CO 2 R) on Ag surfaces and found that they produce no effect on CO 2 R activity yet strongly promote the competing hydrogen evolution reaction (HER). By examining the dependence of HER and CO 2 R rates on concentrations of CO 2 and HCO 3 –, we developed a kinetic model that attributes HER promotion to intrinsic promotion of HCO 3 – reduction by imidazolium ionomers. We also show that varying the ionomer structure by changing substituents on the imidazolium ring modulates the HER promotion. This ionomer-structure dependence was analyzed via Taft steric parameters and density functional theory calculations, which suggest that steric bulk from functionalities on the imidazolium ring reduces access of the ionomer to both HCO 3 – and the Ag surface, thus limiting the promotional effect. Our results help develop design rules for ionomer–catalyst interactions in CO 2 R and motivate further work into precisely uncovering the interplay between primary and secondary coordination in determining electrocatalytic behavior.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Valence Band Modification and High Thermoelectric Performance in SnTe Heavily Alloyed with MnTe

Herein we demonstrate a high solubility limit of >9 mol% for MnTe alloying in SnTe. The electrical conductivity of SnTe decreases gradually while the Seebeck coefficient increases remarkably with increasing MnTe content, leading to enhanced power factors. The room-temperature Seebeck coefficients of Mn-doped SnTe are significantly higher than those predicted by theoretical Pisarenko plots for pure SnTe, indicating a modified band structure. The high-temperature Hall data of Sn 1– x Mn x Te show strong temperature dependence, suggestive of a two-valence-band conduction behavior. Moreover, the peak temperature of the Hall plot of Sn 1– x Mn x Te shifts toward lower temperature as MnTe content is increased, which is clear evidence of decreased energy separation (band convergence) between the two valence bands. The first-principles electronic structure calculations based on density functional theory also support this point. The higher doping fraction (>9%) of Mn in comparison with ~3% for Cd and Hg in SnTe gives rise to a much better valence band convergence that is responsible for the observed highest Seebeck coefficient of ~230 μV/K at 900 K. The high doping fraction of Mn in SnTe also creates stronger point defect scattering, which when combined with ubiquitous endotaxial MnTe nanostructures when the solubility of Mn is exceeded scatters a wide spectrum of phonons for a low lattice thermal conductivity of 0.9 W m –1 K –1 at 800 K. The synergistic role that Mn plays in regulating the electron and phonon transport of SnTe yields a high thermoelectric figure of merit of 1.3 at 900 K.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗