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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 271 records · Page 15

Selective concentration of multivalent cations via electrodialysis through tandem membranes

Selective electrodialysis is attractive for recovering and recycling valuable ions. However, most studies in this field focus on membranes that are selective for monovalent ions. Multivalent cations preferentially partition into cation-exchange membranes, but low mobilities and concentration polarization limit electrodialysis selectivities for these cations. This work employs electrodialysis through an “in-series” combination of a Nafion membrane and a multilayer polyelectrolyte film (MPF)-coated Nafion membrane to concentrate and isolate La 3+ or Mg 2+ from monovalent ions. The bare Nafion membrane gives a La 3+ /Na + selectivity up to 4 (depending on conditions), which enables concentration of La 3+ with a high current efficiency. The MPF-coated membrane allows selective passage of Na + while rejecting La 3+ to increase the purity of the concentrated multivalent cation. For example, the concentration of La 3+ in the accumulation solution can reach 9 times its original concentration in the feed solution with a purity of 93 mol% (99 wt%) when starting with equimolar mixtures of NaNO 3 and La(NO 3 ) 3 . This study examines how the separation varies with the type of polyelectrolyte, the applied voltage, and the composition of feed, accumulation, and cathode solutions. Here, a high nitric acid concentration (0.5 M) in the cathode compartment allows monovalent anions to pass through the MPF-coated Nafion membrane to maintain the electroneutrality of the accumulation solution. With a low acid concentration (0.04 M) in the cathode chamber, water splitting occurs at the MPF-coated membrane and La(OH) 3 precipitates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Curious Case of Pu + : Insight on 5f Orbital Activity from Inductively Coupled Plasma Tandem Mass Spectrometry (ICP-MS/MS) Reactions

A comprehensive understanding of when and how 5f orbitals participate in complex chemical bonding is important for a variety of applications. The actinides are unique in that they possess 5f orbitals and can access high oxidation states, which make them attractive for use in catalysis. Fundamental studies of actinide–ligand interactions offer a mechanism to examine the activation of the 5f orbitals so that the selectivity of 5f orbitals can be assessed. A previous study examined the reaction of Pu + + CO 2 and determined that the reaction efficiency is restricted by a barrier, namely, promotion from the Pu + ground-state configuration, 5f 6 7s, to a reactive-state configuration, 5f 5 6d 2 . Here, the present study illustrates the benefit of activation of Pu’s 5f orbitals when studying the reaction of Pu + + NO. In this reaction, PuO + forms in an exothermic, barrierless process. The 5f orbitals can and do participate in forming a linear intermediate, [N-Pu-O] + , and this drives the exothermic reaction. Understanding the conditions under which 5f orbitals are active in chemical bonding is the key to exploiting the actinides’ selective catalytic capabilities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrolyte–Electrocatalyst Interfacial Effects of Polymeric Materials for Tandem CO 2 Capture and Conversion Elucidated Using In Situ Electrochemical AFM

Integrating CO 2 capture and electrochemical conversion has been proposed as a strategy to reduce the net energy required for CO 2 regeneration in traditional CO 2 capture and conversion schemes and can be coupled with carbon-free renewable electricity. Polyethylenimine (PEI)-based materials have been previously studied as CO 2 capture materials and can be integrated in these reactive capture processes. PEI-based electrolytes have been found to significantly increase the CO 2 loading, and impact selectivity and rate of product formation when compared to the conventional aqueous electrolytes. However, the influence of these materials at the catalyst–electrode interface is currently not well understood. In this study, PEI-based electrolytes were prepared and their impact on the morphology of a silver electrode performing electrochemical CO 2 reduction (CO 2 R) was studied using in situ electrochemical atomic force microscopy (EC-AFM). The presence of PEI on the electrode surface could be distinguished based on nanomechanical properties (DMT modulus), and changes were observed as negative polarization was applied, revealing a reorganization of the PEI chains due to electrostatic interactions. These changes were impacted by the electrolyte composition, including the addition of supporting electrolyte KHCO 3 salt, as well as CO 2 captured by the PEI-based electrolyte, which minimized the change in surface mechanical properties and degree of PEI alignment on the electrode surface. The changes in surface mechanical properties were also dependent on the PEI polymer length, with higher molecular weight PEI showing different reconfiguration than the shorter polymer brushes. The study highlights that the choice of polymer material, the electrolyte composition, and CO 2 captured impact the nearelectrode environment, which has implications for CO 2 R, and presents EC-AFM as a new tool that can be used to probe the dynamic behavior of these interfaces during electrocatalysis.

36 MATERIALS SCIENCE↗