SEARCH · Engineering Papers

Results for “superoxide”

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.

SourceResearch connectionFrom yearThrough year

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 415 records · Page 23

All sources NASA NTRS DOE OSTI

DOE OSTI2020

Beyond Strain: Controlling the Surface Chemistry of CsPbI 3 Nanocrystal Films for Improved Stability against Ambient Reactive Oxygen Species

Colloidal halide perovskite nanocrystals (NCs) have the possibility of easy scale-up due to their batch synthesis and have demonstrated excellent optoelectronic properties. In particular, perovskite NCs have remarkably high photoluminescence quantum yields in solution and as thin films and impressive open circuit voltages in photovoltaic devices. Despite these promising results, little work has been done to understand the stability of CsPbI 3 NCs for optoelectronic device applications. It has been previously shown that the ligands impart tensile surface strain, which stabilizes the black three-dimensional (3D) perovskite phase against phase degradation, making CsPbI 3 NCs some of the most structurally robust inorganic halide perovskites to date. However, understanding exactly how CsPbI 3 NCs degrade under ambient conditions is critical. Additionally, we demonstrate that the degradation mechanism of NCs is unique from, and 2 orders of magnitude slower than, their polycrystalline thin-film counterparts. Under specific conditions, CsPbI 3 NC films show a compositional instability instead of the phase instability seen in large grain CsPbI 3 . This is mediated through reactions with superoxide and other reactive oxygen species, which are initiated from surface defect states, O 2 and light. We then use this mechanistic insight to identify multiple strategies to prolong the lifetimes of CsPbI 3 NC films, by going beyond surface strain to mitigate key surface chemistries. We demonstrate that (1) minimizing the number of surface defects (2) using an alkylammonium bromide ligand surface treatment and (3) encapsulation with an oxygen scavenging layer all increase NC film lifetimes by inhibiting various steps in the photo-oxidation degradation reaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2016

Iron-Mediated Oxidation of Methoxyhydroquinone under Dark Conditions: Kinetic and Mechanistic Insights

Despite the biogeochemical significance of the interactions between natural organic matter (NOM) and iron species, considerable uncertainty still remains as to the exact processes contributing to the rates and extents of complexation and redox reactions between these important and complex environmental components. Investigations on the reactivity of low-molecular-weight quinones, which are believed to be key redox active compounds within NOM, toward iron species, could provide considerable insight into the kinetics and mechanisms of reactions involving NOM and iron. Here in this study, the oxidation of 2-methoxyhydroquinone (MH 2 Q) by ferric iron (Fe(III)) under dark conditions in the absence and presence of oxygen was investigated within a pH range of 4-6. Although Fe(III) was capable of stoichiometrically oxidizing MH 2 Q under anaerobic conditions, catalytic oxidation of MH 2 Q was observed in the presence of O 2 due to further cycling between oxygen, semiquinone radicals, and iron species. A detailed kinetic model was developed to describe the predominant mechanisms, which indicated that both the undissociated and monodissociated anions of MH 2 Q were kinetically active species toward Fe(III) reduction, with the monodissociated anion being the key species accounting for the pH dependence of the oxidation. The generated radical intermediates, namely semiquinone and superoxide, are of great importance in reaction-chain propagation. In conclusion, the kinetic model may provide critical insight into the underlying mechanisms of the thermodynamic and kinetic characteristics of metal-organic interactions and assist in understanding and predicting the factors controlling iron and organic matter transformation and bioavailability in aquatic systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2018

Photochemical Formation and Transformation of Birnessite: Effects of Cations on Micromorphology and Crystal Structure

As important components with excellent oxidation and adsorption activity in soils and sediments, manganese oxides affect the transportation and fate of nutrients and pollutants in natural environments. In this work, birnessite was formed by photocatalytic oxidation of Mn 2+ aq in the presence of nitrate under solar irradiation. The effects of concentrations and species of interlayer cations (Na + , Mg 2+ , and K + ) on birnessite crystal structure and micromorphology were investigated. The roles of adsorbed Mn 2+ and pH in the transformation of the photosynthetic birnessite were further studied. The results indicated that Mn 2+ aq was oxidized to birnessite by superoxide radicals (O 2 •– ) generated from the photolysis of NO 3 – under UV irradiation. The particle size and thickness of birnessite decreased with increasing cation concentration. The birnessite showed a plate-like morphology in the presence of K + , while exhibited a rumpled sheet-like morphology when Na + or Mg 2+ was used. The different micromorphologies of birnessites could be ascribed to the position of cations in the interlayer. The adsorbed Mn 2+ and high pH facilitated the reduction of birnessite to low-valence manganese oxides including hausmannite, feitknechtite, and manganite. Finally, this study suggests that interlayer cations and Mn 2+ play essential roles in the photochemical formation and transformation of birnessite in aqueous environments.

36 MATERIALS SCIENCE↗

DOE OSTI2019

Solar Irradiation Induced Transformation of Ferrihydrite in the Presence of Aqueous Fe 2+

Ferrihydrite commonly occurs in soils and sediments, especially in acid mine drainage (AMD). Solar irradiation may affect Fe(II)-catalyzed transformation of metastable ferrihydrite to more stable iron oxides on AMD surface. We investigated the Fe(II)-catalyzed transformation process and mechanism of ferrihydrite under light irradiation. In nitrogen atmosphere, Fe 2+ aq could be oxidized to goethite and lepidocrocite by hydroxyl radical (OH • ), superoxide radical (O 2 •– ) and hole (h vb + ) generated from ferrihydrite under ultraviolet (UV) irradiation (300–400 nm) at pH 6.0, and O 2 •– and h vb + were mainly responsible for Fe 2+ aq oxidation. In addition, the ligand-to-metal charge-transfer (LMCT) process between Fe(II) and ferrihydrite could be promoted by UV irradiation. Goethite proportion increased with increasing Fe 2+ aq concentration. Both visible (vis) and solar irradiation could also lead to the oxidation of Fe 2+ aq to goethite and lepidocrocite, and the proportion of lepidocrocite increased with increasing light intensity. Fe 2+ aq was photochemically oxidized to schwertmannite at pH 3.0 and 4.5, and the oxidation rate was higher than that under dark conditions in air. The photochemical oxidation rate of Fe 2+ aq decreased in the presence of humic acid. This study facilitates a better understanding of the formation and transformation of iron oxides in natural environments and ancient Earth.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2025

Radiation Effects on Uranyl Tetrachloro Coordination Compounds: Impact of Lattice Water

Nuclear materials, such as uranium-bearing solids, are exposed to high levels of ionizing radiation throughout the nuclear fuel cycle; thus, it is important to develop a molecular-level understanding of how these materials behave and degrade in the presence of gamma (γ) irradiation. In the current study, three U(VI) tetrachloride complexes, M 2 [UO 2 Cl 4 ]·xH 2 O (where M = K + , Rb + , or Cs + and x = 0 or 2), and their respective chloride salts were exposed to 1–50 kGy of γ radiation using a 60 Co source. Irradiated materials were evaluated by using electron paramagnetic resonance (EPR) and Raman spectroscopy and were further explored by using density functional theory (DFT) methods. EPR spectra of the irradiated materials suggest the formation of a Cl-based radical for both the alkali salts and the uranyl tetrachloride compounds, and DFT calculations provide evidence that the Cl 2 –• radical is formed within these materials. The presence of water in the K + and Rb + compounds leads to additional spectroscopic signatures that could be traced back to water radiolysis and the formation of peroxide and superoxide species. DFT results support the formation of HO 2 • in the lattice and potentially the formation of a [UO 2 Cl 3 (O 2 )] 3– species, highlighting the impact of water within the hydrated material to alter U(VI) speciation by radiolysis.

36 MATERIALS SCIENCE↗

DOE OSTI2020

A Computational Assessment of Actinide Dioxide Cations AnO 2 2+ for An = U to Lr: The Limited Stability Range of the Hexavalent Actinyl Moiety, [O=An=O] 2+

The isolated gas-phase actinide dioxide dications, AnO 2 2+ , were evaluated by DFT and coupled cluster CCSD(T) calculations for 12 actinides, An = U–Lr. CASSCF calculations were used to define the orbitals for the CCSD(T) calculations. The characteristic linear [O$=$An$=$O] 2+ hexavalent actinyl(VI) was found to be the lowest energy structure for An = U, Np, and Pu, which also form stable actinyl(VI) species in solution and possibly for Am when spin–orbit effects are included. For Am, there is a divalent [An II (O 2 )] 2+ structure where the dioxygen is an end-on physisorbed η 1 - 3 O 2 2 kcal/mol above the actinyl when spin–orbit effects are included which lower the energy of the actinyl structure. For An = Cm, Bk, and Lr, the lowest energy structure is trivalent [An III (O 2 – )] 2+ where the dioxygen is a side-on superoxide, η 2 -O 2 – . For Cm, the actinyl is close in energy to the ground state when spin–orbit effects are included. For An = Cf, Es, Fm, Md, and No, the lowest energy structure is divalent [An II (O 2 )] 2+ where the dioxygen is an end-on physisorbed η 1 - 3 O 2 . The relative energies suggest that curyl(VI) and berkelyl(VI), like well-known americyl(VI), might be stabilized by coordinating ligands in condensed phases. The results further indicate that for californyl and beyond, the actinyl(VI) moieties will probably be elusive even using strong donor ligands. The prevalence of low oxidation states (OSs) An(II) and An(III) for transplutonium actinides reflects stabilization of the 5f orbitals and validates established trends, including the remarkably high stability of divalent No. Finally, bond distances and other parameters suggest maximum bond covalency around plutonyl(VI), with a particularly substantial decrease in bond strength between americyl(VI) and curyl(VI).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2017

Heptavalent Actinide Tetroxides NpO 4 – and PuO 4 – : Oxidation of Pu(V) to Pu(VII) by Adding an Electron to PuO 4

The highest known actinide oxidation states are Np(VII) and Pu(VII), both of which have been identified in solution and solid compounds. Recently a molecular Np(VII) complex, NpO 3 (NO 3 ) 2 -, was prepared and characterized in the gas phase. In accord with the lower stability of heptavalent Pu, no Pu(VII) molecular species has been identified. Reported here are the gas-phase syntheses and characterizations of NpO 4 - and PuO 4 - . Reactivity studies and density functional theory computations indicate the heptavalent metal oxidation state in both. This is the first instance of Pu(VII) in the absence of stabilizing effects due to condensed phase solvation or crystal fields. Here, the results indicate that addition of an electron to neutral PuO 4 , which has a computed electron affinity of 2.56 eV, counterintuitively results in oxidation of Pu(V) to Pu(VII), concomitant with superoxide reduction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Cyanine-Incorporated Amorphous Polymeric Carbon Dots for Optical Reactive Oxygen Species Sensing

Reactive oxygen species (ROS) are common cellular oxidants that when overproduced by cellular stressors cause harm to cells. Detection of ROS is of utmost importance to understanding a wide variety of cellular function and toxicity mechanisms. Conventional ROS fluorescence assays involve using a single dye to visualize the ROS quantity. Herein, we describe ROS-sensitive, fluorescent-dye-incorporated carbon dots with dual fluorescence capabilities and good biocompatibility. Carbon dots (CDs) made of citric acid and urea were synthesized with incorporated cyanine-3-amine (Cy3), a bright red fluorescent dye, to create Cy3-CDs. Additionally, to get Cy3 into the ROS-sensitive form, this work demonstrated that Cy3 alone and Cy3 within carbon dots can be electrochemically reduced to their colorless ROS-sensitive form. Cy3, CDs, and Cy3-CDs are all responsive to additions of superoxide, leading to an increase in the fluorescence. Overall, this work examines how O 2 •– and additional oxidizers interact with CDs, Cy3, and Cy3-CDs, and molecular-level hypotheses are explored that will inform the design of future carbon dot-based ROS sensors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2016

Effect of Silver Nanoparticles on the Photophysics of Riboflavin: Consequences on the ROS Generation

Metal-enhanced singlet oxygen, O 2 ( 1 Δg), generation is a desirable effect to augment the amount of O 2 ( 1 Δg) produced upon irradiation of organic sensitizers. Herein, we employed pectin for stabilizing 9 nm silver nanoparticles and showed that these particles are able to form a ground-sate complex with riboflavin (Rf). Pump–probe transient absorption spectroscopy and laser flash-photolysis experiments proved that the excited state of the riboflavin–Ag complex feeds the triplet state of the sensitizer, which results in an enhanced intersystem crossing process. We note the higher amounts of riboflavin triplet states formed in the presence of the nanoparticles result in higher yields of singlet oxygen and hydrogen peroxide produced in the irradiated colloidal suspensions. As a result, not only the effect on singlet oxygen but also the effect on superoxide radical ion should contribute to a better performance of Riboflavin as a sensitizer applied to the photodynamic therapy of tumors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Li 8 MnO 6 : A Novel Cathode Material with Only Anionic Redox

In Li-excess transition-metal-oxide cathode materials, anionic oxygen redox can offer high capacity and high voltages, although peroxo and superoxo species may cause oxygen loss, poor cycling performance, and capacity fading. Previous work showed that undesirable formation of peroxide and superoxide bonds is controlled to some extent by Mn substitution, and the present work uses density functional calculations to examine the reasons for this by studying the anionic redox mechanism Li 8 MnO 6 . This material is obtained by substituting Mn for Sn in Li 8 SnO 6 or for Zr in Li 8 ZrO 6 , and we also compare to previous work on those materials. The calculations predict that Li 8 MnO 6 is stable at room temperature (with a band gap of 3.19 eV as calculated HSE06 and 1.82 eV as calculated with the less reliable with PBE+U), and they elucidate the chemical and structural effects involved in the inhibition of oxygen release in this cathode. Throughout the whole delithiation process, only O 2- ions are oxidized. The directional Mn-O bonds formed from unfilled 3d orbitals effectively inhibit the formation of O-O bonds, and the layered structure is maintained even after removing 3 Li per Li 8 MnO 6 formula unit. The calculated average voltage for removal of 3 Li is 3.69 V by HSE06, and the corresponding capacity is 389 mAh/g. The high voltage of oxygen anionic redox and the high capacity result in a high energy density of 1436 Wh/kg. The Li-ion diffusion barrier for the dominant interlayer diffusion path along the c-axis is 0.57 eV by PBE+U. Finally, these results help us to understand the oxygen redox mechanism in a new lithium-rich Li 8 MnO 6 cathode material and contribute to the design of high-energy-density lithium-ion-battery cathode materials with favorable electrochemical properties based on anionic oxygen redox.

Li8MnO6↗

DOE OSTI2021

Tandem Catalytic Antioxidant Nanoparticles Comprising Cerium Carbonate and Photoactive Metal Oxides

While photoactive metal oxides such as TiO 2 find widespread use in paints and coatings as well as cosmetics and suncare products, they also generate reactive oxygen species (ROS), which degrade materials and are associated with human-health pathologies. Here, we demonstrate a robust and potent catalytic antioxidant consisting of earth-abundant cerium carbonate nanoparticles and micron-size Ce 2 (CO 3 ) 3 . 8H 2 O, which are characterized by powder X-ray diffraction and scanning nanobeam electron diffraction. When dispersed with photoactive metal oxides, these cerium carbonate catalysts decrease the photodecomposition rate of organic dyes and commercial pigment colorants in aqueous media by up to 820-fold, as well as in acrylic coatings. X-ray photoelectron spectroscopy and kinetic experiments support the same tandem catalysis mechanism of photoprotection when using both micron-size Ce 2 (CO 3 ) 3 . 8H 2 O and cerium carbonate nanoparticles. This mechanism involves ROS disproportionation (catalyzed by cerium carbonate) and H 2 O 2 decomposition (partially catalyzed by TiO 2 ) pathways, both of which cerium carbonate also catalyzes on its own, crudely mimicking the function of the cascade system of superoxide dismutase and catalase enzymes. When cerium carbonate nanoparticles were dispersed at 2 wt % in polymethylmethacrylate, the transparency of the polymer film was preserved and the photo-oxidative degradation of the polymer was prevented following UV irradiation at 254 nm, which otherwise resulted in the loss of optical properties and hydroxylation as characterized by ATR-FTIR spectroscopy, in the control polymer lacking cerium carbonate. Similar observations were made regarding color preservation in paint films comprising dye and insoluble commercial colorant pigments. The material chemistry associated with this photoprotection catalysis is subtle and emphasizes the importance of both Ce(III) and carbonate together, as both CePO 4 and Na 2 CO 3 are inactive. In conclusion, this emphasis is also apparent in comparisons of photoprotection catalysis with previously reported cerium oxide nanoparticles, which are significantly less active compared with Ce 2 (CO 3 ) 3 . 8H 2 O under the same conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

How a Formate Dehydrogenase Responds to Oxygen: Unexpected O 2 Insensitivity of an Enzyme Harboring Tungstopterin, Selenocysteine, and [4Fe–4S] Clusters

The reversible two-electron interconversion of formate and CO 2 is catalyzed by both nonmetallo- and metallo-formate dehydrogenases (FDHs). The latter group comprises molybdenum- or tungsten-containing enzymes with the metal coordinated by two equivalents of a pyranopterin cofactor, a cysteinyl or selenocysteinyl (Sec) ligand supplied by the polypeptide, and a catalytically essential terminal sulfido ligand. In addition, these biocatalysts incorporate one or more [4Fe–4S] clusters for facilitating long-distance electron transfer. However, an interesting dichotomy arises when attempting to understand how the metallo-FDHs react with O 2 . Whereas existing scholarship portrays these enzymes as being unable to perform in air due to extreme O 2 lability of their metal centers, studies dating as far back as the 1930s emphasize that some of these systems exhibit formate oxidase (FOX) activity, coupling formate oxidation to O 2 reduction. Therefore, to reconcile these conflicting views, we explored context-dependent functional linkages between metallo-FDHs and their cognate electron acceptors within the same organism vis-à-vis catalysis under atmospheric O 2 . Here, we report the discovery and characterization of an O 2 -insensitive FDH2 from the sulfate-reducing bacterium Desulfovibrio vulgaris Hildenborough (DvH) that ligates tungsten, Sec, and four [4Fe–4S] clusters. By advancing a robust expression platform for its recombinant production, we eliminate both the requirement of nitrate or azide during purification and reductive activation with thiols and/or formate prior to catalysis. Because the distinctive spectral signatures of formate-reduced DvH-FDH2 remain invariant under anaerobic and aerobic conditions, we benchmarked the enzyme activity in air, identifying CO 2 as the catalytic product. Full reaction progress curve analysis discloses a high catalytic efficiency when probed with a high-potential artificial electron acceptor. Furthermore, we show that DvH-FDH2 enables near-stoichiometric hydrogen peroxide production without superoxide release to achieve O 2 insensitivity. Notably, simultaneous electron transfer to cytochrome c and O 2 reveals that metal-based electron bifurcation is operational in this system. Taken together, our work proves the co-occurrence of redox bifurcated FDH and FOX activities within a metalloenzyme scaffold. These findings set the stage for uncovering previously unknown O 2 -insensitive flavin-based electron bifurcation mechanisms, as well as for developing authentic formate/air biofuel cells, engineering O 2 -stable FDHs and biohybrid metallocatalysts, and discerning formate bioenergetics of gut microbiota.

13C NMR↗

DOE OSTI2022

Deciphering the Mechanistic Role of Individual Oxide Phases and Their Combinations in Supported Mn–Na 2 WO 4 Catalysts for Oxidative Coupling of Methane

Oxidative coupling of methane (OCM) is an attractive direct route for upgrading methane to valuable chemicals. In this study, Temporal Analysis of Products (TAP) and steady state experiments are conducted to understand the role of individual oxide phases and their combinations in supported Mn-Na 2 WO 4 /SiO 2 catalysts for OCM. The results from TAP transient kinetic studies indicate that Mn plays an important role in promoting gas phase oxygen activation, while NaO x /SiO 2 and WO x /SiO 2 are relatively inert towards gas phase oxygen and methane activation. However, the supported catalyst combining Na and W in the form Na 2 WO 4 show enhanced gas phase oxygen activation exhibiting a much lower oxygen activation energy (148 kJ/mol) and enhanced activity toward methane activation as compared to the individual supported oxide catalysts. Addition of Mn to Na 2 WO 4 /SiO 2 further decreases the oxygen activation energy by 40 kJ/mol. Moreover, methane activation is also enhanced with CH 3 as the main intermediate but, with increasing Mn content, more CH 2 intermediates are observed. Different forms of oxygen (both dioxygen and atomic) are detected on the catalyst surface using isotopic pump/probe pulsing and their distribution is found to depend on the catalyst composition. An optimal Mn content in the Na 2 WO 4 /SiO 2 catalyst system is needed to enhance the amount of dioxide surface species (e.g., superoxide 16 O 2 - or peroxide 16 O 2 2- ) associated with the Na 2 WO 4 leading to high C 2 selectivity for OCM. When the Mn content is too high, the larger MnOx domains are shown to contribute to the formation of higher concertation of monoxide surface species that lead to nonselective OCM pathways. This insight from transient kinetic characterization using TAP combined with conventional steady state studies, provides a deeper understanding of the role of individual oxide phases and their combination on supported catalysts toward the formation of intermediate surface species and their impact on the OCM reaction mechanism. This knowledge is critical toward designing superior catalyst formulations for OCM.

10 SYNTHETIC FUELS↗

DOE OSTI2019

Anionic Single-Atom Catalysts for CO Oxidation: Support-Independent Activity at Low Temperatures

We study here 14 atomically dispersed transition metals on halite-type oxides (MeO, Me = Fe, Mg, Mn, and Ni) using periodic density functional theory calculations and probe structure and activity toward CO oxidation for a subset of these systems experimentally. Pd and Pt can form stable negatively charged species upon binding to oxygen vacancies; the magnitude of the metal atom binding energy depends on the O vacancy formation energies of the supporting metal oxide and the lattice match between transition metal and support. The resulting oxide-supported single-atom systems catalyze CO oxidation by molecularly adsorbed O 2 with intrinsic barriers as low as 36 kJ/mol for Pt/MnO x (001). This high activity stems from the single sites’ ability to stabilize surface superoxide species. Furthermore, intrinsic barriers were found to depend primarily on the identity of the transition metal and to be nearly independent of the support identity. However, O 2 may heal the oxygen vacancy, which leads to catalyst deactivation. Catalyst deactivation by oxygen can be suppressed by using a more reducible support such as FeO(001) or MnO(001).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2017

Temperature Dependence of the Oxygen Reduction Mechanism in Nonaqueous Li–O 2 Batteries

The temperature dependence of the oxygen reduction mechanism in Li-O 2 batteries was investigated using carbon nanotube-based air electrodes and 1,2-dimethoxyethane-based electrolyte within a temperature range of 20C to 40C. It is found that the discharge capacity of the Li-O 2 batteries decreases from 7,492 mAh g -1 at 40C to 2,930 mAh g -1 at 0C. However, a sharp increase in capacity was found when the temperature was further decreased and a very high capacity of 17,716 mAh g -1 was observed at 20C at a current density of 0.1 mA cm-2. When the temperature increases from 20C to 40C, the morphologies of the Li 2 O 2 formed varied from ultra-small spherical particles to small flakes and then to large flake-stacked toroids. The lifetime of superoxide and the solution pathway play a dominate role on the battery capacity in the temperature range of -20C to 0C, but the electrochemical kinetics of oxygen reduction and the surface pathway dominate the discharge behavior in the temperature range of 0C to 40C. These findings provide fundamental understanding on the temperature dependence of oxygen reduction process in a Li-O 2 battery and will enable a more rational design of Li-O 2 batteries.

25 ENERGY STORAGE↗

DOE OSTI2017

High-Capacity Sodium Peroxide Based Na–O 2 Batteries with Low Charge Overpotential via a Nanostructured Catalytic Cathode

The superoxide based Na-O 2 battery has circumvented the issue of large charge overpotential in Li-O-2 batteries; however, the one-electron process leads to limited capacity. Here in this paper, a sodium peroxide based low-overpotential (similar to 0.5 V) Na-O 2 battery with a capacity as high as 7.5 mAh/cm 2 is developed with Pd nanoparticles as catalysts on the cathode.

25 ENERGY STORAGE↗

DOE OSTI2014

Understanding Side Reactions in K–O 2 Batteries for Improved Cycle Life

Superoxide based metal-air (or metal-oxygen) batteries, including potassium and sodium-oxygen batteries, have emerged as promising alternative chemistries in the metal-air battery family because of much improved round-trip efficiencies (>90%). In order to improve the cycle life of these batteries, it is crucial to understand and control the side reactions between the electrodes and the electrolyte. For potassium-oxygen batteries using ether-based electrolytes, the side reactions on the potassium anode have been identified as the main cause of battery failure. The composition of the side products formed on the anode, including some reaction intermediates, have been identified and quantified. Combined experimental studies and density functional theory (DFT) calculations show the side reactions are likely driven by the interaction of potassium with ether molecules and the crossover of oxygen from the cathode. To inhibit these side reactions, the incorporation of a polymeric potassium ion selective membrane (Nafion-K+) as a battery separator is demonstrated that significantly improves the battery cycle life. The K-O-2 battery with the Nafion-K+ separator can be discharged and charged for more than 40 cycles without increases in charging overpotential.

Ren, Xiaodi↗

DOE OSTI2011

Probing Oxygen Activation Sites in Two Flavoprotein Oxidases Using Chloride as an Oxygen Surrogate

A single basic residue above the si-face of the flavin ring is the site of oxygen activation in glucose oxidase (GOX) (His516) and monomeric sarcosine oxidase (MSOX) (Lys265). Crystal structures of both flavoenzymes exhibit a small pocket at the oxygen activation site that might provide a preorganized binding site for superoxide anion, an obligatory intermediate in the two-electron reduction of oxygen. Chloride binds at these polar oxygen activation sites, as judged by solution and structural studies. First, chloride forms spectrally detectable complexes with GOX and MSOX. The protonated form of His516 is required for tight binding of chloride to oxidized GOX and for rapid reaction of reduced GOX with oxygen. Formation of a binary MSOX-chloride complex requires Lys265 and is not observed with Lys265Met. Binding of chloride to MSOX does not affect the binding of a sarcosine analogue (MTA, methylthioactetate) above the re-face of the flavin ring. Definitive evidence is provided by crystal structures determined for a binary MSOX-chloride complex and a ternary MSOX-chloride-MTA complex. Chloride binds in the small pocket at a position otherwise occupied by a water molecule and forms hydrogen bonds to four ligands that are arranged in approximate tetrahedral geometry: Lys265:NZ, Arg49:NH1, and two water molecules, one of which is hydrogen bonded to FAD:N5. The results show that chloride (i) acts as an oxygen surrogate, (ii) is an effective probe of polar oxygen activation sites, and (iii) provides a valuable complementary tool to the xenon gas method that is used to map nonpolar oxygen-binding cavities.

08 HYDROGEN↗