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NASA NTRS2008

Search for O VI Emission from the Shocked Circurmstellar Gas of SN 1987A

The Far Ultraviolet Spectroscopic Explorer (FUSE) was used to search for broad O VI emission from the shock interaction zones produced by the collision of high-velocity supernova ejecta with the dense inner circumstellar ring of SN 1987A. Since the shock interaction with the inner ring began in 1997, broad (FWHM = 300 km/sec) emission from optical coronal lines (e.g. [Fe X], [Fe XI], and [Fe XIV]) has emerged and increased exponentially in strength. O VI 1032-1038 Angstrom emission is expected to track the coronal lines. O VI is also expected to be the primary cooling transition for the million-degree shocked gas. An accurate measurement of the O VI line strength would significantly improve current models of the shock interaction. FUSE observations of SN 1987A in 2000 and 2001 did not detect broad O VI due to spectral contamination fiom two earlytype stars within a few arc seconds of the SN. However, O VI emission was detected with narrow line widths (FWHM less than 35 km/sec) and a heliocentric radial velocity of +280 km/sec. This places the emitting gas at rest relative to the supernova and is interpreted as emission from unshocked circumstellar gas. A new FUSE observation of SN 1987A obtained in May 2007 used a narrow slit (1.25 x 20 arcsec) to significantly reduce the spectral contamination from the two early-type stars. Yet the 2007 spectrum does not reveal any significant O VI emission. The implications of these results are discussed.

Sonneborn, G.↗

NASA NTRS2014

On Helium-Dominated Stellar Evolution: The Mysterious Role of the O(He)-Type Stars

Context. About a quarter of all post-asymptotic giant branch (AGB) stars are hydrogen-deficient. Stellar evolutionary models explain the carbon-dominated H-deficient stars by a (very) late thermal pulse scenario where the hydrogen-rich envelope is mixed with the helium-rich intershell layer. Depending on the particular time at which the final flash occurs, the entire hydrogen envelope may be burned. In contrast, helium-dominated post-AGB stars and their evolution are not yet understood. Aims. A small group of very hot, helium-dominated stars is formed by O(He)-type stars. A precise analysis of their photospheric abundances will establish constraints to their evolution. Methods. We performed a detailed spectral analysis of ultraviolet and optical spectra of four O(He) stars by means of state-of-the-art non-LTE model-atmosphere techniques. Results. We determined effective temperatures, surface gravities, and the abundances of H, He, C, N, O, F, Ne, Si, P, S, Ar, and Fe. By deriving upper limits for the mass-loss rates of the O(He) stars, we found that they do not exhibit enhanced mass-loss. The comparison with evolutionary models shows that the status of the O(He) stars remains uncertain. Their abundances match predictions of a double helium white dwarf (WD) merger scenario, suggesting that they might be the progeny of the compact and of the luminous helium-rich sdO-type stars. The existence of planetary nebulae that do not show helium enrichment around every other O(He) star precludes a merger origin for these stars. These stars must have formed in a different way, for instance via enhanced mass-loss during their post-AGB evolution or a merger within a common-envelope (CE) of a CO-WD and a red giant or AGB star. Conclusions. A helium-dominated stellar evolutionary sequence exists that may be fed by different types of mergers or CE scenarios. It appears likely that all these pass through the O(He) phase just before they become WDs.

evolution↗

NASA NTRS2014

CO Self-Shielding as a Mechanism to Make O-16 Enriched Solids in the Solar Nebula

Photochemical self-shielding of CO has been proposed as a mechanism to produce solids observed in the modern, O-16 depleted solar system. This is distinct from the relatively O-16 enriched composition of the solar nebula, as demonstrated by the oxygen isotopic composition of the contemporary sun. While supporting the idea that self-shielding can produce local enhancements in O-16 depleted solids, we argue that complementary enhancements of O-16 enriched solids can also be produced via CO-16 based, Fischer-Tropsch type (FTT) catalytic processes that could produce much of the carbonaceous feedstock incorporated into accreting planetesimals. Local enhancements could explain observed O-16 enrichment in calcium-aluminum-rich inclusions (CAIs), such as those from the meteorite, Isheyevo (CH/CHb), as well as in chondrules from the meteorite, Acfer 214 (CH3). CO selfshielding results in an overall increase in the O-17 and O-18 content of nebular solids only to the extent that there is a net loss of CO-16 from the solar nebula. In contrast, if CO-16 reacts in the nebula to produce organics and water then the net effect of the self-shielding process will be negligible for the average oxygen isotopic content of nebular solids and other mechanisms must be sought to produce the observed dichotomy between oxygen in the Sun and that in meteorites and the terrestrial planets. This illustrates that the formation and metamorphism of rocks and organics need to be considered in tandem rather than as isolated reaction networks.

Solar Nebula↗

NASA NTRS2016

Van Allen Probes Observations of Magnetic Field Dipolarization and Its Associated O+ Flux Variations in the Inner Magnetosphere at L 6.6

We investigate the magnetic field dipolarization in the inner magnetosphere and its associated ion flux variations, using the magnetic field and energetic ion flux data acquired by the Van Allen Probes. From a study of 74 events that appeared at L= 4.5-6.6 between 1 October 2012 and 31 October 2013, we reveal the following characteristics of the dipolarization in the inner magnetosphere: (1) its time scale is approximately 5 min; (2) it is accompanied by strong magnetic fluctuations that have a dominant frequency close to the O+ gyrofrequency; (3) ion fluxes at 20-50 keV are simultaneously enhanced with larger magnitudes for O+ than for H+; (4) after a few minutes of the dipolarization, the flux enhancement at 0.1-5 keV appears with a clear energy-dispersion signature only for O+; and (5) the energy-dispersed O+ flux enhancement appears in directions parallel or antiparallel to the magnetic field. From these characteristics, we discuss possible mechanisms that can provide selective acceleration to O+ ions at > 20 keV. We conclude that O+ ions at L= 5.4-6.6 undergo nonadiabatic local acceleration caused by oscillating electric field associated with the magnetic fluctuations and/or adiabatic convective transport from the plasma sheet to the inner magnetosphere by the impulsive electric field. At L= 4.5-5.4, however, only the former acceleration is plausible. We also conclude that the field-aligned energy-dispersed O+ ions at 0.1-5 keV originate from the ionosphere and are extracted nearly simultaneously to the onset of the dipolarization.

Magnetosphere↗

NASA NTRS2018

Interpreting Precession-Driven δ O-18 Variability in the South Asian Monsoon Region

Speleothem records from the South Asian summer monsoon (SASM) region display variability in the ratio of O-18 and O-16 (δ O-18) in calcium carbonate at orbital frequencies. The dominant mode of variability in many of these records reflects cycles of precession. There are several potential explanations for why SASM speleothem records show a strong precession signal, including changes in temperature, precipitation, and circulation. Here we use an Earth system model with water isotope tracers and water-tagging capability to deconstruct the precession signal found in SASM speleothem records. Our results show that cycles of precession-eccentricity produce changes in SASM intensity that correlate with local temperature, precipitation, and δ O-18. However, neither the amount effect nor temperature differences are responsible for the majority of the SASM δ O-18 variability. Instead, changes in the relative moisture contributions from different source regions drive much of the SASM δ O-18 signal, with more nearby moisture sources during Northern Hemisphere summer at aphelion and more distant moisture sources during Northern Hemisphere summer at perihelion. Further, we find that evaporation amplifies the δ O-18 signal of soil water relative to that of precipitation, providing a better match with the SASM speleothem records. This work helps explain a significant portion of the long-term variability found in SASM speleothem records.

paleoclimate↗

NASA NTRS2024

Mechanisms of Apatite Formation in Reactions of Yb 2-2x Gd 2x Si 2 O 7 with CMAS

Bulk β-Yb 1.9 Gd 0.1 Si 2 O 7 , β-Yb 1.6 Gd 0.4 Si 2 O 7 , and γ-Yb 1.4 Gd 0.6 Si 2 O 7 , along with baseline γ-Y 2 Si 2 O 7 and β-Yb 2 Si 2 O 7 were investigated in contact with a molten silicate to determine mechanisms of thermochemical degradation. A model 30.67CaO-8.25MgO-12.81AlO 1.5- 48.27SiO 2 silicate composition was deposited on the surfaces of the samples at a loading of ~2 mg/cm 2 . Reactions with the molten silicate resulted in the formation of a silicate apatite layer, which has been shown to reduce further molten silicate infiltration. Additions of gadolinium up to 30 mol% to Yb 2 Si 2 O 7 reduced infiltration up to ~60% compared to baseline Yb 2 Si 2 O 7 , but additional exposure time at temperature resulted in loss of the apatite layer. The results herein indicate that doping with gadolinium disilicate may not be beneficial in the long term degradation of disilicate-based EBCs by molten silicates.

Jamesa L. Stokes↗

DOE OSTI2020

The Stability of SiO{sub 2} Fe{sub 3}O{sub 4} Nanoparticles for Uranium Extraction in Acidic Media - 20189

This comprehensive study has shown that the proposed strategy of SiO{sub 2} coating of Fe{sub 3}O{sub 4} nanoparticles (NPs) for the use of uranium (U) extraction in acidic media was successful. The breakdown of Fe{sub 3}O{sub 4} in acidic media has proven to be a challenge when applying to a nuclear waste removal scenario, leading to the dissolution of Fe{sub 3}O{sub 4} and preventing uptake of U ions in the waste. To overcome this a SiO{sub 2} passivating layer was grafted to the Fe{sub 3}O{sub 4} NPs, to which an acid stability test was conducted between pH 3 and pH 4. It has been shown via Transmission Electron Microscopy (TEM) and zeta potential measurements that the uncoated Fe{sub 3}O{sub 4} NPs exhibit rapid coagulation when exposed to acidic conditions, moving from a stable zeta potential of -44 mV to an unstable zeta potential of +6 mV. SiO{sub 2} coated Fe{sub 3}O{sub 4} on the other hand can remain stable for several hours and continue to be stable beyond that. Throughout acid exposure the zeta potential of these NPs remained at ∼ -38 mV, showing great stability. As a functionality is needed on the surface of the NPs for separation and extraction, the phosphate complex used was also tested for its acid stability. It was determined that with a constant zeta potential of ∼ -20 mV, the phosphate functionality was able to remain stable in the acidic conditions simulating the environment of certain nuclear wastes. Overall SiO{sub 2} coated (PO)x-Fe{sub 3}O{sub 4} NPs show great promise for application in separation and removal of U in acid media. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2020

Temperature-induced changes in the synthesis gas composition in a high-temperature H 2 O and CO 2 co-electrolysis system

Solid oxide electrolysis cell (SOEC) is an attractive renewable technology capable of producing synthesis gas (H 2 + CO) from H 2 O and CO 2 . An SOEC consists of a solid oxide electrolyte and two ceramic or metal-ceramic electrodes. H 2 O and CO 2 are electrolyzed at the cathode producing H 2 and CO, releasing O 2- ions, which travel through the electrolyte to the anode side and recombine to produce pure oxygen gas as the byproduct. In the present study, a La 0.7 Sr 0.2 Ni 0.2 Fe 0.8 O 3 cathode was used to co-electrolyze H 2 O and CO 2 at three different operating temperatures- 700 °C, 750 °C and 800 °C. Synthesis gas was produced at all three operating temperatures with 100% Faradaic efficiency. The composition of the syngas, however, was found to be a function of the operating temperature. In general, the H 2 /CO ratio in the syngas decreased with increased temperature. This was partially due to CO 2 electrolysis becoming more favorable compared to H 2 O electrolysis at higher temperatures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Unravelling the sintering temperature-induced phase transformations in Ba(Fe 0.7 Ta 0.3 )O 3-δ ceramics

This work reports on the fundamental details of the crystal structure and phase transformations in Ba(Fe 0.7 Ta 0.3 )O 3-δ , the best known temperature-independent oxygen-sensing ceramic material for applications in extreme environments. Ba(Fe 0.7 Ta 0.3 )O 3-δ ceramics were synthesized using conventional solid-state ceramic reaction under variable sintering temperatures (T s = 1200–1350 °C). Combined X-ray diffraction (XRD) and high-resolution transmission electron microscopy (TEM) measurements revealed the T s -induced phase transformations and their origin in Ba(Fe 0.7 Ta 0.3 )O 3-δ . Associated with phase transformations, pseudo-cubic (PC) reflections, such as {200} PC , {211} PC , and {220} PC , exhibited distinct anomalies with increasing T s . At T s = 1200 °C, Ba(Fe 0.7 Ta 0.3 )O 3-δ stabilized in mixed orthorhombic + rhombohedral phases (Amm2 + R3m). With increasing T s (≥1250 °C), Ba(Fe 0.7 Ta 0.3 )O 3-δ ceramics stabilized in tetragonal/rhombohedral [P4mm + R3m] mixed phases, while variations in the quantity of the respective phases were observed. Because both structure and crystal chemistry play key roles in achieving enhanced performance in chemical sensing and catalytic converters, detailed understanding of the phase transformations and crystal structure of Ba(Fe 0.7 Ta 0.3 )O 3-δ ceramics, as derived in this work, will be useful to develop chemical sensors with optimum performance for high-temperature and corrosive environments.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Engineering shallow and deep level defects in $\kappa$-Ga 2 O 3 thin films: comparing metal-organic vapour phase epitaxy to molecular beam epitaxy and the effect of annealing treatments

Orthorhombic gallium oxide (κ-Ga 2 O 3 ) is an ultra-wide bandgap semiconductor with great potential in new generation electronics. Its application is hindered at present by the limited physical understanding of the relationship between synthesis and functional properties. This work discusses the effects of growth method (metal-organic vapour phase epitaxy and molecular beam epitaxy) as well as annealing treatments in different atmospheres (O 2 , H 2 ) on point defects in κ-Ga 2 O 3 layers epitaxially grown on c-plane sapphire. Comprehensive experimental characterization by X-ray diffraction, photo current-as well as photoluminescence excitation spectroscopy, and X-ray photo electron spectroscopy is combined with first principles calculations of the point defects’ formation and complex-dissociation energies. We demonstrate that for κ-Ga 2 O 3 the concentration of shallow and deep level defects can be sensitively controlled through annealing treatments at temperatures (T = 500 °C) well below the thermal stability threshold of this polymorph. In particular, our results suggest that hydrogen-related defects (e.g., H-interstitials, Ga-vacancies—H complexes) play a key role in this process. While we provide direct exemplary implications of our results for the performances of κ-Ga 2 O 3 based photodetectors, these findings are predicted to impact further application fields of κ-Ga 2 O 3 , such as high electron mobility transistors or memory devices.

36 MATERIALS SCIENCE↗

DOE OSTI2022

Vacancy-Driven Disorder and Elevated Dielectric Response in the Pyrochlore Pb 1.5 Nb 2 O 6.5

Lone pair-driven distortions are a hallmark of many technologically important lead (Pb)-based materials. Here, the role of Pb 2+ in polar perovskites is well understood and easily manipulated for applications in piezo- and ferroelectricity, but the control of ordered lone pair behavior in Pb-based pyrochlores is less clear. Crystallographically and geometrically more complex than the perovskite structure, the pyrochlore structure is prone to geometric frustration of local dipoles due to a triangular arrangement of cations on a diamond lattice. The role of vacancies on the O' site of the pyrochlore network has been implicated as an important driver for the expression and correlation of stereochemically active lone pairs in pyrochlores such as Pb 2 Ru 2 O 6.5 and Pb 2 Sn 2 O 6 . In this work we report on the structural, dielectric, and heat capacity behavior of the cation- and anion-deficient pyrochlore Pb 1.5 Nb 2 O 6.5 upon cooling. We find that local distortions are present at all temperatures that can be described by cristobalite-type cation ordering, and this ordering persists to longer length scales upon cooling. From a crystallographic perspective, the material remains disordered and does not undergo an observable phase transition. In combination with density function calculations, we propose that the stereochemical activity of the Pb 2+ lone pairs is driven by proximity to O' vacancies, and the crystallographic site disorder of the O' vacancies prohibits long range correlation of lone pair-driven distortions. This in turn prevents a low-temperature phase transition and results in an elevated dielectric permittivity across a broad temperature range.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Hydrogen Stability and Bonding in SiN x and Al 2 O 3 Dielectric Stacks on Poly-Si/SiO x Passivating Contacts

Polycrystalline Si on SiO x passivating contacts enables some of the highest efficiency single-junction Si photovoltaic devices, but the high-temperature firing process needed for industrial metallization can significantly reduce passivation. We show that after firing, the implied open-circuit voltage, iV oc , for the Al 2 O 3 /SiN x /poly-Si/SiO x /c-Si stack is 20-30 mV higher than the SiNx/Al 2 O 3 /poly-Si/SiO x /c-Si stack and therefore provides better passivation of the SiO x /c-Si interface. Using effusion measurements and Fourier transform infrared spectroscopy, we demonstrate that more than twice as much hydrogen is retained in the dielectric up to the peak firing temperature of ~800 degrees C for Al 2 O 3 -capped structures. If the Al 2 O 3 layer is not present in the stack, after firing, the iVoc is lower by 50-100 mV compared to Al 2 O 3 /SiN x or SiN x /Al 2 O 3 stacks. These studies will inform future work on the role of dielectrics in aiding the passivation of poly-Si/SiO x passivating contacts.

08 HYDROGEN↗

DOE OSTI2020

Point and extended defects in heteroepitaxial 𝛽−G⁡a 2 ⁢O 3 films

G⁡a 2 ⁢O 3 is emerging as an excellent potential semiconductor for high power and optoelectronic devices. However, the successful development of G⁡a 2⁢ O 3 in a wide range of applications requires a full understanding of the role and nature of its point and extended defects. Here, in this work, high quality epitaxial G⁡a 2 ⁢O 3 films were grown on sapphire substrates by metal-organic chemical vapor deposition and fully characterized in terms of structural, optical, and electrical properties. Then defects in the films were investigated by a combination of depth-resolved Doppler broadening and lifetime of positron annihilation spectroscopies and thermally stimulated emission (TSE). Positron annihilation techniques can provide information about the nature and concentration of defects in the films, while TSE reveals the energy level of defects in the bandgap. Despite very good structural properties, the films exhibit short positron diffusion length, which is an indication of high defect density and long positron lifetime, a sign for the formation of Ga vacancy related defects and large vacancy clusters. These defects act as deep and shallow traps for charge carriers as revealed from TSE, which explains the reason behind the difficulty of developing conductive G⁡a 2 ⁢O 3 films on non-native substrates. Positron lifetime measurements also show nonuniform distribution of vacancy clusters throughout the film depth. Further, the work investigates the modification of defect nature and properties through thermal treatment in various environments. It demonstrates the sensitivity of G⁡a 2 ⁢O 3 microstructures to the growth and thermal treatment environments and the significant effect of modifying defect structure on the bandgap and optical and electrical properties of G⁡a 2 ⁢O 3 .

defects↗

DOE OSTI2020

Density Functional Theory Study of the Initial Stages of Cl-Induced Degradation of α -Cr 2 O 3 Passive Film

The ion exchange and point defect models are two prominent models describing the role of anions, such as chlorides, in the degradation of passive oxide films. Here the thermodynamic feasibility of critical steps of Cl-induced degradation of a hydroxylated α-Cr 2 O 3 (0001) surface, as proposed by these two models, are studied. Both models begin with Cl substitution of surface OH and H 2 O, which becomes less favorable with increasing Cl coverage. The initial stages of Cl-induced breakdown of the α-Cr 2 O 3 depend on Cl coverage and the presence of O vacancy near the surface as follows: (1) neither Cl insertion (supporting the ion exchange model) nor Cr vacancy formation (supporting the point defect model) is feasible at low Cl coverages except in the presence of O vacancies near the surface, where Cl insertion is thermodynamically feasible even at low coverages, (2) in the absence of O vacancies, Cr vacancy formation becomes feasible from 10/12 ML onwards whereas Cl insertion by exchange with subsurface OH only becomes feasible at full coverage. This implies that at higher coverages Cl-induced degradation first initiates through a vacancy formation mechanism, but both insertion and vacancy formation would be feasible at full coverage.

36 MATERIALS SCIENCE↗

DOE OSTI2024

E. coli -expressed SECRET AGENT O -GlcNAc modifies threonine 829 of GIGANTEA

The Arabidopsis thaliana glycosyl transferases SPINDLY (SPY) and SECRET AGENT (SEC) modify nuclear and cytosolic proteins with O-linked fucose or O-linked N-acetylglucosamine (O-GlcNAc), respectively. O-fucose and O-GlcNAc modifications can occur at the same sites. SPY interacts physically and genetically with GIGANTEA (GI), suggesting that it could be modified by both enzymes. Previously, we found that, when co-expressed in Escherichia coli, SEC modifies GI; however, the modification site was not determined. By analyzing the overlapping sub-fragments of GI, we identified a region that was modified by SEC in E. coli. Modification was undetectable when threonine 829 (T829) was mutated to alanine, while the T834A and T837A mutations reduced the modification, suggesting that T829 was the primary or the only modification site. Mapping using mass spectrometry detected only the modification of T829. Previous studies have shown that the positions modified by SEC in E. coli are modified in planta, suggesting that T829 is O-GlcNAc modified in planta.

59 BASIC BIOLOGICAL SCIENCES↗

NASA NTRS1995

Observations of downward moving O(+) in the polar topside ionosphere

New investigations of the core ion motion within high-latitude topside ionosphere and near-Earth magnetosphere, using data from the Dynamics Explorer (DE) retarding ion mass spectrometer (RIMS), reveal the existence of significant regions of downward moving O(+). The occurences of downgoing versus upgoing O(+) are not clearly separable in terms of either polar zenith angle or Kp but are well distinquished by the direction of the z component of the interplanetary magnetic field (IMF). On the average, down flow dominates when IMFB2 less than O, while upflow dominates for IMFB2 greater than 0. Combining cross-field convection velocities derived from an empirical convection electric field model with the observed parallel velocities yields a two dimensional ion velocity field. This velocity field is consistent with a senario which has O(+) of cusp/cleft and auroral zone origin concvecting into the polar cap and, because of the dominance of gravitational energy over the upward kinetic energy, falling back into the inonsphere. This provides additional confirmation of the results of studies of the cleft ion fountain. Estimates of the flux of O(+) in the upflowing and downflowing regions for Lambda greater than or equal to 60 deg give a total upflow of approximately 6 X 10(exp 25) ions/sec for IMFB2 greater than 0 and total upflow and downflow of approximately 4 X 10 (exp 25) ions/sec and 1 x 10(exp 25) ions/sec, respectively, for IMFB less than 0. In all cases the magnitude of the dayside outflow is consistent with previous work on upwelling ions. While the magnitudes vary for high and low Kp the ratios of upward to downward flow are roughly the same at approximately 1.7. The downflowing O(+) shows a correlation with the magnitude of the outflow of light ions in the same region but the cause and effect of this relationship is not distinquishable. hable.

Chandler, M. O.↗

DOE OSTI2021

Novel nucleocytoplasmic protein O -fucosylation by SPINDLY regulates diverse developmental processes in plants

Here, in metazoans, protein O-fucosylation of Ser/Thr residues was only found in secreted or cell surface proteins, and this post-translational modification is catalyzed by ER-localized protein O-fucosyltransferases (POFUTs) in the GT65 family. Recently, a novel nucleocytoplasmic POFUT, SPINDLY (SPY), was identified in the reference plant Arabidopsis thaliana to modify nuclear transcription regulators DELLAs, revealing a new regulatory mechanism for gene expression. The paralog of AtSPY, SECRET AGENT (SEC), is an O-link-N-acetylglucosamine (GlcNAc) transferase (OGT), which O-GlcNAcylates Ser/Thr residues of target proteins. Both AtSPY and AtSEC are tetratricopeptide repeat-domain-containing glycosyltransferases in the GT41 family. The discovery that AtSPY is a POFUT clarified decades of miss-classification of AtSPY as an OGT. SPY and SEC play pleiotropic roles in plant development, and the interactions between SPY and SEC are complex. SPY-like genes are conserved in diverse organisms, except in fungi and metazoans, suggesting that O-fucosylation is a common mechanism in modulating intracellular protein functions.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2023

Fe-N 4 O-C Nanoplates Covalently Bonding on Graphene for Efficient CO 2 Electroreduction and Zn-CO 2 Batteries

Electrochemical carbon dioxide (CO 2 ) reduction into value-added products holds great promise in moving toward carbon neutrality but remains a grand challenge due to lack of efficient electrocatalysts. Herein, the nucleophilic substitution reaction is elaborately harnessed to synthesize carbon nanoplates with a Fe-N 4 O configuration anchored onto graphene substrate (Fe-N 4 O-C/Gr) through covalent linkages. Density functional theory calculations demonstrate the unique configuration of Fe-N 4 O with one oxygen (O) atom in the axial direction not only suppresses the competing hydrogen evolution reaction, but also facilitates the desorption of *CO intermediate compared with the commonly planar single-atomic Fe sites. The Fe-N 4 O-C/Gr shows excellent performance in the electroreduction of CO 2 into carbon monoxide (CO) with an impressive Faradaic efficiency of 98.3% at -0.7 V versus reversible hydrogen electrode (RHE) and a high turnover frequency of 3511 h -1 . Furthermore, as a cathode catalyst in an aqueous zinc (Zn)-CO 2 battery, the Fe-N 4 O-C/Gr achieves a high CO Faradaic efficiency (≈91%) at a discharge current density of 3 mA cm -2 and long-term stability over 74 h. Here this work opens up a new route to simultaneously modulate the geometric and electronic structure of single-atomic catalysts toward efficient CO 2 conversion.

25 ENERGY STORAGE↗