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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 19 records

Effect of Pressure and Temperature on Carbon Dioxide Reduction at a Plasmonically Active Silver Cathode

Here, carbon dioxide reduction at a plasmonically active silver cathode was investigated by varying the pressure and temperature at multiple applied potentials under both dark and illuminated conditions to understand the mechanism of selectivity changes driven by plasmon-enhanced electrochemical conversion. Carbon dioxide partial pressures (P Co 2 ) from 0.2 to 1 atm were studied during linear sweep voltammetry and chronoamperometry at -0.7, -0.9, and -1.1 V RHE . At a given applied overpotential the total current density increased with increasing P Co 2 in both the dark and the light, but there were significant differences in the Tafel behavior between dark and illuminated conditions. The reduction of CO 2 to carbon monoxide (CO) was found to have first-order behavior with respect to P Co 2 at all applied potentials in both the dark and the light, likely indicating no change in the rate-determining step upon illumination. Activity for the hydrogen (H 2 ) evolution reaction decreased with increasing P Co 2 at slightly different rates in the dark and the light at each applied potential, making it unclear if light is influencing CO or H 2 intermediate adsorbate coverage. Both formate and methanol production showed no dependence on P Co 2 under any conditions, but the true reaction orders may be masked by the much higher activity for CO and H 2 at the silver cathode. The investigation of product distribution with temperature at 14, 22, and 32°C at -0.7, -0.9, and -1.1 V RHE in both the dark and the light demonstrated that the selectivity changes observed upon illumination are not caused by local heating of the cathode surface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Preparation of silver-activated zinc sulfide thin films

Silver improves luminescence and reduces contamination of zinc sulfide phosphors. The silver is added after the zinc sulfide phosphors are deposited in thin films by vapor evaporation, but before calcining, by immersion in a solution of silver salt.

Feldman, C.↗

Tin sensitization and silver activation on indium tin oxide surfaces

Adhesion of electrical contacts on electronic and optoelectronic devices is important for reliable device operation. Sn-sensitization is a widely used process that improves uniformity and adhesion of plated metals to glass and polymer surfaces. Electrically conductive substrates can significantly benefit from improved uniformity, adhesion, and contact resistance to metallic contact layers. In this study, we investigate the process of Sn-sensitization and Ag-activation on indium tin oxide (ITO) surfaces—a dominant transparent conducting oxide used in optoelectronic devices. Here, our results show that ITO films exposed to Sn-sensitization solutions with HCl concentrations below 10 mM effectively modify the surface termination through the process of Sn-sensitization (Sn-bonding at the surface hydroxide sites) without etching the ITO film. However, the subsequent Ag-activation on an ITO surface does not seem to follow the typical response on a glass substrate, suggesting that Ag-activation of an ITO surface is likely limited by the Ag ion size relative to the area density of surface hydroxide sensitization sites.

42 ENGINEERING↗

Preliminary investigation of a sealed, remotely activated silver-zinc battery

Methods necessary to provide a remotely activated, silver zinc battery capable of an extended activated stand while in a sealed condition were investigated. These requirements were to be accomplished in a battery package demonstrating an energy density of at least 35 watt hours per pound. Several methods of gas suppression were considered in view of the primary nature of this unit and utilized the electroplated dendritic zinc electrode. Amalgamation of the electrode provided the greatest suppression of gas at the zinc electrode. The approach to extending the activated stand capability of the remotely activated battery was through evaluation of three basic methods of remote, multi-cell activation; 1) the electrolyte manifold, 2) the gas manifold and 3) the individual cell. All three methods of activation can be incorporated into units which will meet the minimum energy density requirement.

Wheat, C. G.↗

Reduction of carbon dioxide at a plasmonically active copper–silver cathode

Electrochemically deposited copper nanostructures were coated with silver to create a plasmonically active cathode for carbon dioxide (CO 2 ) reduction. Illumination with 365 nm light, close to the peak plasmon resonance of silver, selectively enhanced 5 of the 14 typically observed copper CO 2 reduction products while simultaneously suppressing hydrogen evolution. At low overpotentials, carbon monoxide was promoted in the light and at high overpotentials ethylene, methane, formate, and allyl alcohol were enhanced upon illumination; generally C 1 products and C 2 /C 3 products containing a double carbon bond were selectively promoted under illumination. Temperature-dependent product analysis in the dark showed that local heating is not the cause of these selectivity changes. Finally, while the exact plasmonic mechanism is still unknown, these results demonstrate the potential for enhancing CO 2 reduction selectivity at copper electrodes using plasmonics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Development and Characterization of Cementitious Waste Forms for Immobilization of Granular Activated Carbon, Silver Mordenite, and HEPA Filter Media Solid Secondary Waste

At the Department of Energy’s Hanford site, over 53 million gallons of chemically complex and radioactive wastes have been stored in 177 underground tanks. The Hanford Tank Waste Treatment and Immobilization Plant (WTP) is under construction and is designed to treat and immobilize these wastes. During operations of WTP, solid secondary wastes (SSWs) will be generated as a result of waste treatment, vitrification, off-gas management, and supporting process activities. SSW treatment processes and resulting disposal pathways for the final disposition form of the SSW are needed to support direct feed low activity waste (DFLAW) operations and facilitate continued operation of WTP. The SSWs produced through WTP operations are expected to include used process equipment, contaminated tools and instruments, decontamination wastes, high-efficiency particulate air (HEPA) filters, carbon absorption beds (granular activated carbon, GAC), silver mordenite (AgM) and spent ion-exchange resins. These waste streams are planned to be immobilized in a cementitious waste form and disposed of either as stabilized/blended (non-debris) or encapsulated (debris) in a cementitious waste form. Accordingly, cementitious waste forms from these streams were included in the 2017 Integrated Disposal Facility (IDF) Performance Assessment (PA). The input data used to represent these SSW forms in the 2017 IDF PA involved many assumptions and associated uncertainties. This data limitation was due to the lack of material- and site-specific data available for representative SSW materials in cementitious matrices. To verify the assumed values used in the IDF PA and fill this limitation in available data, Washington River Protection Solutions, LLC (WRPS), has initiated a program targeted toward gathering site specific data relevant to Hanford SSW disposal. The work within this report is a continuation of this ongoing program.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Polydopamine Surface Coating Synergizes the Antimicrobial Activity of Silver Nanoparticles

Metal nanoparticles, especially silver nanoparticles (AgNPs), have drawn increasing attention for antimicrobial applications. Most studies have emphasized on the correlations between the antibacterial potency of AgNPs and the kinetics of metallic to ionic Ag conversion, while other antimicrobial mechanisms have been underestimated. In this work, we focused on the surface effects of polydopamine (PDA) coating on the antimicrobial activity of AgNPs. A method of fast deposition of PDA was used to synthesize the PDA-AgNPs with controllable coating thickness ranging from 3 to 25 nm. The antimicrobial activities of the PDA-AgNPs were analyzed by fluorescence-based growth curve assays on Escherichia coli. The results indicated that the PDA-AgNPs exhibited significantly higher antibacterial activities than poly(vinylpyrrolidone)-passivated AgNPs (PVP-AgNPs) and PDA themselves. It was found that the PDA coating synergized with the AgNPs to prominently enhance the potency of the PDA-AgNPs against bacteria. Additionally, the analysis of X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy elucidated that the synergistic effects could be originated from the interaction/coordination between Ag and catechol group on the PDA coating. The synergistic effects led to increased generation of reactive oxygen species and the consequent bacterial damage. Overall, these findings demonstrated the importance of the surface effects on the antimicrobial properties of AgNPs. The underlying molecular mechanisms have shined light on the future development of more potent metal nanoparticle-based antimicrobial agents.

36 MATERIALS SCIENCE↗

Twin Knudsen Cell Configuration for Activity Measurements by Mass Spectrometry

A twin Knudsen cell apparatus for alloy activity measurements by mass spectrometry is described. Two Knudsen cells - one containing an alloy and one containing a pure component - are mounted on a single flange and translated into the sampling region via a motorized x-y table. Mixing of the molecular beams from the cells is minimized by a novel system of shutters. Activity measurements were taken on two well-characterized alloys to verify the operation of the system. Silver activity measurements are reported for Ag-Cu alloys and aluminum activity measurements are reported for Fe-Al alloys. The temperature dependence of activity for a 0.474 mol fraction Al-Fe alloy gives a partial molar heat of aluminum. Measurements taken with the twin cell show good agreement with literature values for these alloys.

Jacobson, N. S.↗

Plasmonic Ag nanocomposite phosphate glasses produced via γ-ray irradiation as reduction route

This paper reports on the impact of γ-ray irradiation (10, 100 kGy) on melt-quenched Ag + -doped phosphate glass and the effects of subsequent thermal processing leading to the production of plasmonic Ag nanocomposites. The γ-irradiated glasses were characterized alongside the pristine by differential scanning calorimetry (DSC), Raman spectroscopy, electron paramagnetic resonance (EPR) spectroscopy, optical absorption, and photoluminescence (PL) spectroscopy. DSC characterization showed consistent glass transition temperatures (T g ) before and after γ-irradiation whereas the crystallization temperatures tended to decrease with increasing γ-ray dose. However, a lack of alteration of the glass network structure was supported by Raman spectroscopy. Room temperature EPR spectra clearly showed the formation of phosphorus oxygen hole center (POHC) defects in the undoped host, in addition to another doublet likely associated with a P 3 defect. The presence of paramagnetic silver species encompassing Ag 2+ and 107/109 Ag 0 atoms was also indicated in the silver-activated glass together with POHC defects. Optical absorption spectra were also consistent with the presence of various radiation-induced centers. Further analyzing the glass absorption edge via Tauc plots suggested the formation of electron center (EC) defects in γ-irradiated samples wherein the silver-doped glass exhibited decreasing band gap energies with increasing γ-ray dose. The PL characterization showed the silver-related radio-PL effect was induced exhibiting broad band emission with two maxima around 500 and 625 nm stemming from various molecular Ag$^{x+}_{n}$ clusters. Emission decay analyses revealed that the longer wavelength emission exhibited slower decay. The highest radiation dose of 100 kGy however resulted in weaker emission and faster decay kinetics attributed to energy transfer between the luminescent silver species and POHC defects. Finally subjecting the γ-irradiated Ag-doped glasses to heat treatment near the T g at 490 °C led to the development of the surface plasmon resonance of Ag nanoparticles (NPs) and the vanishing of the Ag$^{x+}_{n}$ clusters luminescence. In conclusion, the presence of the matrix-related EC defects was deemed accountable for the thermally induced reduction and consequent precipitation of Ag NPs making the plasmonic glasses attractive for photonic applications such as nonlinear optics.

36 MATERIALS SCIENCE↗

Engineering metal–metal oxide surfaces for high-performance oxygen reduction on Ag–Mn electrocatalysts

Understanding fundamental material–property relationships in mixed-element catalyst systems is crucial to advancing the viability of renewable electrochemical energy technologies, an important part of creating a more sustainable future. Herein, we report our insight on the nature and dynamics of highly active silver–manganese oxide (Ag–MnOx) catalyst surfaces for the oxygen reduction reaction (ORR) via a combined experimental–theoretical approach. Experimentally, we synthesize well-mixed Ag–Mn co-deposited thin films that are measurably flat and smooth, despite Mn surface migration and oxidation upon air exposure and electrochemical measurements. Cyclic voltammetry in 0.1 M KOH demonstrates up to 10-fold specific activity enhancements over pure Ag at 0.8 V vs. RHE for Ag-rich films (70–95% Ag in bulk). To further understand the Ag–Mn system, separate samples were synthesized with small amounts of Mn sequentially deposited onto the surface of a pure Ag thin film (Mn@Ag), ranging from partial to full surface coverage (down to 0.3 nm Mn $cm^{-2}_{geo}$ ~ 0.2 μg Mn $cm^{-2}_{geo}$). These sequentially deposited Mn@Ag films show analogous performance to their co-deposited counterparts indicating similar enhanced active sites. With density functional theory (DFT), we calculate that this enhancement arises from the tuned d-band of these material surfaces owing to the optimal hybridization of the electronic structures in specific Ag and MnO x geometries. Together, electrochemical measurements, DFT calculations, X-ray absorption spectroscopy, and valence-band X-ray photoelectron spectroscopy suggest synergistic electronic interactions between Ag and MnOx yield enhanced oxygen adsorption, and thus ORR activity, with DFT highlighting the Ag–MnO x interface sites as the most enhanced. This work demonstrates how combined experimental–theoretical methods can help design electrocatalysts with enhanced electrocatalytic properties and understand the nature of complex mixed metal–metal oxide surfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Anisotropy of the neutron fluence from a plasma focus.

The fluence of neutrons from a plasma focus was measured by gamma spectrometry of an activated silver target. This method results in a significant increase in accuracy over the beta-counting method. Multiple detectors were used in order to measure the anisotropy of the fluence of neutrons. The fluence was found to be concentrated in a cone with a half-angle of 30 deg about the axis, and to drop off rapidly outside of this cone; the anisotropy was found to depend upon the total yield of neutrons. This dependence was strongest on the axis. Neither the axial concentration of the fluence of neutrons nor its dependence on the total yield of neutrons is explained by any of the currently proposed models. Some other explanations, including the possibility of an axially distributed source, are considered.

Lee, J. H.↗