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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 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Electrocatalytic benchmarking of ruthenium-based bimetallic anodes for the electrocatalytic oxidation of biomass-derived wastewater

In this paper, we report on the synthesis, characterization, and use of ruthenium oxide (RuO 2 ) doped with a secondary metal (M2) to enhance electrochemical activity and stability for the electrocatalytic oxidation (ECO) of biomass-derived wastewaters. We used different electrochemical methods such as cyclic voltammetry (CV), electrochemical surface area (ECSA), and Tafel analysis as well as physical characterization such as grazing incidence X-ray diffraction, X-ray photoelectron spectroscopy, and scanning electron microscopy to understand how the introduction of M2 affects electrochemical performance. Our results show that including an M2 improves the ECO performance regardless of the composition of the electrolyte. Specifically, we saw increase in ECSA, which could be due to enhanced charge transfer for the pH ranges evaluated. Furthermore, the introduction of organic compounds in wastewater generated during the hydrothermal liquefaction of food waste affected the ECO performance differently, depending on M2, the electrolyte composition, and anodic half-cell potential, highlighting the need to properly control the reaction conditions when testing and characterizing the electrocatalysts under different reaction regimes. We developed an in situ electrocatalytic benchmarking protocol, Boruah – Lopez-Ruiz – Strange (BLoRS), to quickly assess if the presence of M2 improves the ECO performance; thus, saving time and resources in ex situ characterization, testing, and product analysis. This foundational work provides the basis for characterization and benchmarking of electrodes of the ECO of organic compounds.

Electrocatalysis↗
DOE OSTI2021

Manipulating cobalt oxide on N-doped aligned electrospun carbon nanofibers towards instant electrochemical detection of dopamine secreted by living cells

A demand exists for the development of miniaturized biosensors with high sensitivity and a wide dynamic range for rapid detecting dopamine (DA) levels. Here, an electrochemical sensor is created by decorating closely packed cobalt oxide (Co 3 O 4 ) nanograins on nitrogen-doped electrospun carbon nanofibers (NECNFs) via a facile electrodeposition method. The carbon nanofiber matrix provides both a scaffold with ultrahigh surface area for homogeneous dispersion of cobalt oxide nanostructures and facilitates the electrochemical conductivity for the hybrid electrode. The sensing principle is based on the redox reaction between DA and DA quinone that generates electrical signal, which is detectable via differential pulse voltammetry (DPV) and chronoamperometry (CA). Owing to a high electroactive surface area and facilitating electron transfer between electrode surface and the target molecule, the electrical sensing platform exhibits superior sensitivity and selectivity toward DA, with an excellent limit of detection (9 nM) over a wide range of concentrations (0.01 to 100 μM). Moreover, based on its excellent sensing properties and biocompatibility, the sensor has been used for the real-time monitoring exogeneous DA released from pheochromocytoma (PC12) cells. This work demonstrates promise of a novel sensor technology that may render rapid point-of-care testing of DA towards early clinical diagnosis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Efficient BiVO 4 /CoFeO x H y photoanodes using controlled annealing and conformal linear-sweep electrocatalyst photodeposition

Although monoclinic bismuth vanadate (BiVO 4 ) is a promising photoanode for solar water splitting, its practical use is hindered by imperfect photocurrent generation/collection, low photovoltage compared to the bandgap, and corrosion side reactions that limit durability. Here, we introduce a controlled-annealing sol–gel process for BiVO 4 thin-film photoanodes along with an optimized linear-sweep-voltammetry photodeposition of CoFeO x H y cocatalysts. The resulting BiVO 4 films annealed at 550 °C exhibited a photocurrent density of 4.1 mA/cm 2 at 1.23 V RHE under 1 sun AM 1.5G solar simulation and a low onset potential of 0.26 V RHE due to high majority carrier conductivity, a crystalline bulk with reduced defects as evidenced by x-ray photoelectron spectroscopy and photoluminescence lifetime analysis, and thus enhanced photocarrier collection. However, significant degradation in performance was found due to interfacial photocorrosion. To protect the surface and speed the oxygen-evolution reaction CoFeO x H y cocatalyst layers were deposited. By varying the number of consecutive sweeps and adjusting the applied bias range, an ultra-thin (~15 nm) CoFeO x H y cocatalyst layer was uniformly grown deposited over 30 cycles on the BiVO 4 surface. The resulting BiVO 4 /CoFeO x H y yielded 4.03 mA/cm 2 at 1.23 V RHE and onset potential of 0.24 V RHE , with stable operation (~15 % loss in photocurrent at 1.23 V RHE relative to ~60 % loss in the uncatalyzed control sample). These conformal CoFeO x H y catalytic layers function simultaneously to selectively collect photoexcited holes from the BiVO 4 , catalyze the water-oxidation reaction, and protect the BiVO 4 from photodegradation.

42 ENGINEERING↗
DOE OSTI2020

Keratin-derived functional carbon with superior charge storage and transport for high-performance supercapacitors

In this work, we report a scalable method to synthesize hierarchically porous, hetero-atom doped activated carbon nanosheet from waste biomass-human hair, and demonstrates the use of this carbon as an ultra-high performance electrode material for supercapacitor applications. Microscopic analyses reveal that sheet size ranges from 50 to 200 nm having a thickness of 15–27 nm. As-synthesized, carbon nanosheets possess a hierarchical porous structure having a specific surface area of 1548 m 2 g -1 . Heteroatom concentration (nitrogen, oxygen, and sulfur) of around 25% is confirmed from XPS analysis. Therefore, the novel interconnected hierarchical porous nanosheets structure enables fast adsorption and transportation of ions during electrochemical processes. Also, the abundant chemically available electroactive heteroatom species in the material enhance the wettability of ions and contribute to pseudocapacitance. The electrochemical analyses through cyclic voltammetry and galvanostatic charge-discharge measurements in 6 M KOH reveal the quasi-EDLC behavior of the activated carbons due to the presence of heteroatoms. A reprensentative KOH activated carbon shows an excellent specific capacitance value of 999 F g -1 at a current density of 1 A g -1 . Furthermore, the symmetrically assembled two-electrode device also delivers a maximum energy density of 32 W h Kg -1 at a power density of 325 W Kg -1 . In addition, excellent cyclic stability of 98% capacitance retention is observed after 10,000 continuous GCD cycles even at a high current density of 5 A g -1 . Symmetric flexible supercapacitor device using KOH-PVA-K3FeCN6 as redox gel polymer electrolyte shows a synergistic specific capacitance of 145 mF cm -1 at a current density of 0.8 mA cm -1 exhibiting very less deviation in bending mode. Therefore, this waste biomass derived heteroatom doped hierarchical porous carbon nanosheets can be a promising material for cost-effective high- performance supercapacitor.

42 ENGINEERING↗
DOE OSTI2021

Carbon aerogels with integrated engineered macroporous architectures for improved mass transport

Carbon aerogels (CAs) combine unique properties including ultra-high surface area, high electrical conductivity, corrosion resistance, and robust mechanical properties making them ideal materials for electrochemical applications. Traditional CA synthesis results in isotropic, random nanoporous networks that work well for applications relying on diffusional mass transport. However, many applications would benefit from integration of engineered macroporous network structures that enable directed pressure-gradient-driven mass transport. In this study, we report on using 3D-printed sacrificial polymeric templates to generate templated CAs (t-CAs) with integrated engineered nonrandom macroporous network structures. Specifically, we used projection micro-stereo-lithography (PμSL) and two-photon polymerization direct laser writing (2PP-DLW) to fabricate millimeter-to-centimeter-sized 3D sacrificial polymeric templates with features ranging from tens of microns (PμSL) to 100s of nanometers (2PP-DLW). T-CAs were fabricated by infiltrating the templates with resorcinol-formaldehyde (RF) precursor solution, followed by carbonization at 1050 °C to simultaneously convert the RF gel to a CA and decompose the 3D-printed template, leaving an embedded templated macroporous network structure behind. X-ray computer tomography confirms integration of the macroporous architecture defined by the template. The templated macroporous architecture improves mass transport in t-CAs compared to traditional bulk CA as demonstrated by more uniform activation and their response in electrochemical cyclic voltammetry and galvanostatic charge-discharge tests.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Direct extracellular electron transfer for high electricity production by a new type of marine microalgae Nannochloropsis sp. HDY2

A growing number of autotrophic microalgae have been found to have extracellular electron transfer (EET) capabilities. However, the mechanism and function of EET pathway in microalgae have not thoroughly investigated. This study presents evidence of direct extracellular electron transfer (DEET) for impressive electricity production by a new type of marine microalgae Nannochloropsis sp. HDY2 in the single and double-chamber photosynthetic microbial fuel cells (PFMCs). The electricity generation of Nannochloropsis sp. is strongly inhibited by photosynthetic inhibitors, suggesting that electrons involved in the extracellular electron transfer (EET) of Nannochloropsis sp. are derived from photosynthesis. The results of dialysis bag and supernatant experiments suggest that Nannochloropsis sp. produce electricity by DEET. The lack of typical redox peaks in cyclic voltammetry (CV) analysis and the appearance of extracellular filamentous component (EFC) around cells support this finding. Under high light conditions, the chlorophyll a and carotenoid content of Nannochloropsis sp. rapidly decreased while the fatty acid synthesis and electricity generation increased, suggesting that the DEET pathway play an active role in the resistance to photooxidation of Nannochloropsis sp. In conclusion, this study provides the first evidence that Nannochloropsis has the capability of performing EET and sheds new light on the positive role of DEET on the environmental adaptation of Nannochloropsis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Oxadiazole derivatives as stable anolytes for >3 V non-aqueous redox flow battery

Effective utilization of energy from renewable sources such as wind and solar requires the development of long duration energy storage (LDES) systems that can accommodate intermittent energy accrual. One option under investigation is the use of a redox flow battery (RFB). A significant amount of work has explored aqueous RFB systems with a variety of inorganic and organic carriers. However, moving to a nonaqueous solvent such as acetonitrile (MeCN) for RFB provides a much larger electrochemical window, which could lead to increased energy density if properly utilized. Here, in this work, we investigate a series of 2,5-diphenyl-1,3,4-oxadiazole (DiPhenOx) derivatives as anolytes for a redox flow battery. DiPhenOx has a low voltage redox event that, while reversible by cyclic voltammetry, was determined to be irreversible during bulk electrolysis. To improve cycling performance, we introduced various ester and cyano groups to the phenyl rings of DiPhenOx using molecular engineering. We characterized these derivatives spectroscopically and electrochemically to assess their feasibility for flow battery applications. The ester derivatives with the best cycling performance were tested in a flow cell vs. ferrocene, 2,5-di-tert-butyl-1,4-bis(2-methoxyethoxy)benzene (DBBB) and thianthrene, which resulted in ~2 V, ~3 V and ~3 V redox flow batteries, respectively.

25 ENERGY STORAGE↗
DOE OSTI2020

Shot noise sets the limit of quantification in electrochemical measurements

Detection of single molecules, particles, and rapid redox events is a challenge of electrochemical investigations and requires either an amplification strategy or significant averaging for the electrochemical current to exceed the noise level. We consider the minimum number of electrons required to reach the limit of quantification in these electrochemical measurements. A survey of the literature indicates that the state-of-the-art limit in current detection for different types of measurements (e.g. voltammetry, single-molecule redox cycling, ion channel recordings of single molecules, metal nanoparticle collision, and phase nucleation) is independent of the nature of the measurement and increases linearly with reciprocal response time, Δt -1 , over ~5 orders of magnitude (from ~10 to ~10 6 s -1 ). This paper demonstrates that the practical limit of quantification requires cumulative measurement of ~2100 electrons during Δt and is determined by statistics of counting electrons, that is, the shot noise in the current.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

An In Situ , multi-electrode electrochemical method to assess the open circuit potential corrosion of Cr in unpurified molten FLiNaK

An in situ electrochemical method to investigate the time-dependent spontaneous corrosion of pure Cr in an unpurified LiF-NaF-KF eutectic salt at 600 °C was developed. A multi-electrode electrochemical cell and a dual-electrode method were utilized to detect Cr(II) and Cr(III) ions on a platinum working electrode using cyclic voltammetry as a function of exposure time and compensating for the distance from the Cr electrode. XRD was performed to characterize the crystalline composition of the exposed FLiNaK and the salt films formed on the working electrodes. The fate of all electro-oxidized Cr must be accounted for to quantify corrosion rates. The concentrations of Cr(II) and Cr(III) species obtained were compared with the gravimetric mass change and ICP-OES analysis of the residual salt. Finally, outcomes, difficulties, and limitations are discussed.

ICP-OES↗
DOE OSTI2026

Nano zero valent iron electrodeposition at boron doped diamond electrodes

Here, in this study, we present an ecofriendly and simple electrochemical method for synthesizing nano zero-valent iron particles (nZVIs) directly on boron-doped diamond (BDD) electrode surfaces. A BDD electrode served as the substrate for electrodeposition using a 5 mM FeCl 3 /0.1 M KCl solution and chronoamperometry at an applied potential of −1.3 V versus Ag/AgCl (1 M KCl), as determined by cyclic voltammetry (CV) and supported by Pourbaix diagram analysis. The electrochemical behavior and surface modification were characterized using CV, electrochemical impedance spectroscopy (EIS), and surface analysis and microscopy techniques. The results confirm that BDD electrodes can serve as effective platforms for a controlled deposition of 56 nm nZVIs, offering a promising strategy for the development of advanced materials for environmental remediation, catalysis, and sensing applications.

36 MATERIALS SCIENCE↗
DOE OSTI2019

An investigation on the impact of halidization on substituted dimethoxybenzenes

Functionalized organic molecules are emerging as charge storage materials in electrochemical technologies as the breadth and diversity of the organic design space offers the possibility of purpose-built materials with property sets optimized for a particular application. First developed as overcharge protection materials in lithium-ion batteries, substituted dialkoxybenzenes represent a potentially promising molecular platform for advancing soluble charge storage materials. In this study, we systematically substitute a series of halide groups at the 2- and 5-positions of the 1,4-dimethoxybenzene core, investigate the impact the halide groups have on molecular properties using electrochemical and spectroscopy methods, and compare these results to those of 2,5-dimethyl-1,4-dimethoxybenzene (25DDB), a previously reported derivative. In general, we observe that introduction of heavy halogen atoms leads to decreased gravimetric capacity as compared to 25DDB, but concomitantly improves solubility and redox potentials. As the halide functional group increases in size, the active material becomes less stable in its oxidized state as evinced by both cyclic voltammetry and bulk electrolysis cycling. None of the halogenated species are as stable as 25DDB indicating that these materials may be better suited for applications with more rapid cycling conditions (e.g., redox shuttling). More broadly, these results may serve as a useful data set for computational methods for materials discovery and optimization.

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

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↗
DOE OSTI2021

Electrolyte effects on the electrochemical performance of microemulsions

Here, we report a study of the electrochemistry of Ferrocene (Fc) in a Tween®20 (polyethylene glycol (20) sorbitan monolaurate) /1-butanol/ water/Toluene (TBWT) microemulsion system, focusing on the effects of electrolyte components. Resistance and conductivity measurements are used along with Cyclic Voltammetry (CV) to characterize the effects of supporting electrolyte, such as Bu 4 NBF 4 and KNO 3 , on the electrochemical performance and transport properties of Fc. With increasing Fc-containing oil phase concentration in the microemulsion, the observed peak current density fails to increase proportionately with the Fc concentration. Adding 0.05 m Bu 4 NBF 4 in the oil phase significantly increases the current density, presumably by lowering the resistance of microemulsion and promoting the accessibility of Fc in the system. Moreover, increasing the aqueous phase supporting electrolyte from 0.5 m KNO 3 to 1 m KNO 3 does not exhibit an analogous effect. We discuss these results in the context of our working hypothesis for microemulsion organization and its implications for electron transfer to Fc.

Conductivity↗
DOE OSTI2022

Carbon nanotubes decorated with Pt as a viable electrocatalyst system using electrochemical atomic layer deposition

Surface limited redox replacement (SLRR) is an electrochemical deposition method designed to deposit metal thin films, typically onto other metals, that are mere monolayers in thickness, where such low dimensions allows catalyst-support interactions to affect catalyst efficiency. Here we explore the growth of Pt, using iterative Cu-mediated SLRR cycles, directly onto carbon nanotubes (CNTs) which are potentially good candidates as electrocatalyst supports due to their electrical conductivity and chemical resistance. Here scanning electron microscope images showed that Pt grew as nanoparticles, and hydrogen underpotential deposition from cyclic voltammetry showed that the active surface area approached an asymptotic value around eight iterations. Catalytic activity, measured using the oxygen reduction reaction, reached a maximum at ten iterations. Both are shown to be influenced by the growth mode, but electrochemical modeling indicates that the trend in activity is also due to a change in activation energy, possibly due to changes in Pt electronic structure due to interactions with the CNTs. Durability cycling showed a greater than 85% retention of surface area for the first 10,000 cycles of accelerated stress testing but decayed steadily to about 50% after 30,000 cycles. This performance may be related to the phenomenon that limits surface area growth.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Selective pseudocapacitive immobilization of REE elements on carbon based electrodes

Current extraction technologies for rare earth elements at ambient conditions are reagent and energy intensive, giving rise to significant quantities of secondary waste streams. Exploration of the removal of common cations from aqueous streams has been undertaken with carbon materials and have shown promising results. However, those promising materials have not been explored extensively for rare earth element capture from aqueous process streams. In this study, a carbon electrode was investigated for the adsorption and immobilization of REE elements from aqueous solutions. Cyclic voltammetry studies of the carbon electrode displayed a pseudocapacitive behavior where it was verified that cation adsorption is accompanied by an electron transfer process. Preliminary tests showed that a current density of 89.1 mA. g -1 , allowed for the pseudocapacitive adsorption (PSA) of Nd 3+ cation without the formation of rare earth hydroxides. Hence, the selective PSA of Nd 3+ was verified in an electrolyte solution with equimolar concentrations of Nd 3+ , Mg 2+ , Li + , Na + and K + , achieving separation factors of 8.6, 1.1, and 10.9 for Nd 3+ /Li + , Nd 3+ /Na + , and Nd 3+ /Mg 2+ , respectively. Analysis of the potential-time curves for the various cations suggests that storage of ions in the electrode involved pore-spacings rather than interlayer spacings and was corroborated by XRD analysis. Specific capacitance as high as >640 F.g -1 for Nd 3+ was also observed for the carbon electrode, with Faradaic efficiencies (FE) of > 20% for Nd 3+ and Mg 2+ , and > 9% for Na + . Furthermore, adsorption capacity of >125 mg g -1 after 4hrs of electrosorption was observed for Nd 3+ . In the presence of the Nd 3+ electrolyte, the electrode achieved increasing storage of Nd 3+ with >94% retention of Nd 3+ with a FE > 20% over 6 cycles between loading and releases in 1 M KCl solution. In conclusion, these preliminary results provide information and some guidance on the selective recovery of rare earth elements, such as Nd, in aqueous streams in the presence of competitive cations employing the use of carbon-based materials.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2025

Electrochemical stability and corrosion behavior of Ni-Cr alloy in molten LiCl-KCl salt

This study investigated the electrochemical properties and potential-dependent stability of Cr(II) and Ni(II) in a eutectic LiCl-KCl molten salt at 500 °C under an argon atmosphere using a three-electrode cell configuration with a glassy carbon working electrode, Ag/Ag + reference electrode, and graphite counter electrode. Cyclic voltammetry was employed to characterize the Cr(0)/Cr(II)/Cr(III) and Ni(0)/Ni(II) redox transitions, yielding diffusion coefficients of 0.50 (±0.01) × 10 −5 cm 2 s −1 for Cr(II) and 0.91 (±0.16) × 10 −5 cm 2 s −1 for Ni(II) at 500 °C. The redox stability domains of these species provided insight into the corrosion mechanisms of a Ni-Cr alloy (80–20 wt %) in LiCl-KCl salt. The measured open circuit potential of the alloy corresponded to the range of potentials where the Ni(0) and Cr(II) species are stable, indicating a preferential dissolution of Cr. Immersion testing of the alloy for 336 h confirmed significant Cr depletion (or Ni-enrichment) at the surface layer, corroborating Cr dealloying as the dominant corrosion reaction under open circuit conditions. Additionally, the application of a small anodic overpotential (0.11 V) resulted in selective Cr dissolution while a large anodic overpotential (0.25 V) resulted in co-dissolution of both Cr and Ni. Furthermore, these results demonstrate that the corrosion mechanisms of a Ni-Cr alloy in LiCl-KCl depend upon the applied potential, and thus the redox conditions of the molten salt should be carefully controlled in the design of a redox buffer to mitigate corrosion in molten salt environments.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2026

Preparation of a uranium monocarbide anode and electrochemical characterization in molten LiCl-KCl-UCl 3

Porous uranium carbide (UC) pellets possessing moderate electrical conductivity were synthesized by reaction of UO 2 with graphite at temperatures up to 1550°C under rough vacuum. Conversions as high as 98% were achieved at soak times of 2-4 hours. The electrochemistry of the UC pellets in molten LiCl-KCl-6.5 wt% UCl 3 was explored using a variety of techniques including DC polarization methods, cyclic voltammetry, chronopotentiometry and bulk electrolysis. Here, the electrode reaction for anodic dissolution was found to be kinetically controlled by dissociation of UC to a transition state complex that was hypothesized to consist of a uranium atom partially complexed by chloride ions. Precise measurements of current efficiencies using chronopotentiometry indicated upper limits of 90.9 ± 3.4% and 98.3 +1.7/-3.7% for anode and cathode, respectively, when operating at anodic overpotentials near +300 mV. Bulk electrolysis of a UC pellet performed by passing 98% of the theoretical charge resulted in nearly complete recovery of its uranium content as highly pure metal at the cathode.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Reduction of uranyl and uranyl-organic complexes mediated by magnetite and ilmenite: A combined electrochemical AFM and DFT study

Reduction of mobile aqueous uranyl complexes can be hindered by the strength of the uranyl-ligand complex and the resistivity of the complexes to electron transfer. Semiconducting solids, such as magnetite (Fe 3 O 4 ) and ilmenite (FeTiO 3 ), can facilitate otherwise-slow electron transfer between the reductant and oxidant, especially if these species are adsorbed on their surfaces as inner-sphere complexes. Electrons can then be shuttled through the surface or the structure. This process can be facilitated by either finding a new electron transfer path or by weakening or destroying the ligand-uranyl complex. Using in situ electrochemical atomic force microscopy (EC-AFM), we imaged reduction products of uranyl as mediated by magnetite and ilmenite in the absence or presence of the organic ligands, ethylenediaminetetraacetate (EDTA) and oxalate. In situ images of uranyl reduction show gradual nucleation and growth of reduced uranium on the mineral surfaces with decreasing reduction potentials. X-ray photoelectron spectroscopy (XPS) measurements indicate pentavalent uranium as the dominant uranium species resulting from uranyl reduction mediated by magnetite and ilmenite. The reduction potentials of uranyl-organic species relevant to our reaction system, (U VI O 2 ∙oxalate) 0 and (U VI O 2 ∙HEDTA) - , are derived using quantum–mechanical modeling and compared with the midpoint potentials obtained from cyclic voltammetry measurements. The spectroscopic, electrochemical, and computational data suggest that the catalysis of Fe-bearing minerals facilitates the reduction of uranyl-organic complexes. U(VI)-oxalate complexes are redox-active and participate directly in the reduction mediated by magnetite. In the presence of EDTA, reduction of uranyl may proceed in concert with ligand exchange between metals (i.e., U and Fe) on the mineral surface. Finally, the proposed mechanism is the breaking of uranyl-organic bonds upon interaction with the mineral surface followed by the formation of Fe-organic bonds, thereby allowing the reduction of hexavalent uranyl to pentavalent one.

58 GEOSCIENCES↗