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At least 19 records

The Industry Energy Tool (IET): Documentation

Studies of industrial energy use typically mention the sector's heterogeneity and complexity as modelling barriers. One of the more significant impediments to analyzing and building models of U.S. industrial energy use is the lack of current, disaggregated data. The Industry Energy Tool (IET) and its foundational data addresses some of these barriers. The IET uses county-level energy data with stock turnover, energy efficiency, fuel switching, and emissions functionalities to calculate energy use and emissions from agriculture, construction, mining, and manufacturing industries from 2014 to 2050. The IET is an open-source, transparent, and flexible tool for exploring industrial sector energy and emissions scenarios. The IET takes a simplified approach to developing scenario projections of energy and emissions by allowing users to modify pre-populated inputs for achieved energy efficiency, rate of equipment stock turnover, and future penetration renewable electricity. In addition to its transparency and flexibility, the strengths of the IET lie in its geographically- and operationally-disaggregated data set. The IET's foundational data is built on energy data first calculated at the facility- and technology-level for many of the largest energy-using industries. These data are then aggregated to the county and end-use level with other publicly-available data for use in scenarios estimated by the IET.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

The ISO 50001 Impact Estimator Tool (IET 50001 V1.1.4) - User Guide and Introduction to the ISO 50001 Impacts Methodology

ISO 50001-Energy management systems – Requirements with guidance for use, is an internationally developed standard that provides organizations with a flexible framework for implementing an energy management system (EnMS) with the goal of continual energy performance improvement. The ISO 50001 standard was first published in 2011 and has since seen growth in the number of certificates issued around the world, primarily in the industrial (agriculture, manufacturing, and mining) and service (commercial) sectors. Policy makers in many regions and countries are looking to or are already using ISO 50001 as a basis for energy efficiency, carbon reduction, and other energy performance improvement schemes. The Impact Estimator Tool 50001 (IET 50001 Tool) is a computational model developed to assist researchers and policy makers determine the potential impact of ISO 50001 implementation in the industrial and service (commercial) sectors for a given region or country. The IET 50001 Tool is based upon a methodology initially developed by the Lawrence Berkeley National Laboratory that has been improved upon and vetted by a group of international researchers. By using a commonly accepted and transparent methodology, users of the IET 50001 Tool can easily and clearly communicate the potential impact of ISO 50001 for a region or country.

97 MATHEMATICS AND COMPUTING↗

IETS and quantum interference: Propensity rules in the presence of an interference feature

Destructive quantum interference in single molecule electronics is an intriguing phenomenon; however, distinguishing quantum interference effects from generically low transmission is not trivial. In this paper, we discuss how quantum interference effects in the transmission lead to either low current or a particular line shape in current-voltage curves, depending on the position of the interference feature. Second, we consider how inelastic electron tunneling spectroscopy can be used to probe the presence of an interference feature by identifying vibrational modes that are selectively suppressed when quantum interference effects dominate. That is, we expand the understanding of propensity rules in inelastic electron tunneling spectroscopy to molecules with destructive quantum interference.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electron transfer between sorbed Fe(II) and structural Fe(III) in smectites and its effect on nitrate-dependent iron oxidation by Pseudogulbenkiania sp. strain 2002

Studies have shown interfacial electron transfer (IET) between sorbed Fe(II) and structural Fe(III) in clays, but how such process alters their reactivity has not been investigated. Here we studied nitrate reduction by Fe(II)-sorbed nontronite (NAu-2) and montmorillonite (SWy-2) in the presence of an Fe(II)-oxidizer, Pseudogulbenkiania sp. At pH 6 a similar amount of Fe(II) (~1.4% wt) sorbed onto the basal surface of both clays, but with different extents of IET. For NAu-2, because a large fraction of sorbed Fe(II) remained on unreactive basal surface, its reactivity towards nitrate reduction was low. For SWy-2, IET changed majority of sorbed Fe(II) to structural Fe(II), resulting in a higher reactivity. At pH 8 the amount of edge-sorbed Fe(II) to NAu-2 (2.93%) was lower than that on SWy-2 (4.66%), and IET oxidized the majority of NAu-2 sorbed Fe(II) to Fe(III). The resulting IET-induced structural Fe(II) and the remaining fraction of sorbed-Fe(II) as a “magnetite-like” phase were highly reactive towards nitrate. In contrast, because of isolated Fe(III) atoms within the SWy-2 structure, the extent of IET was limited and the majority of sorbed Fe(II) co-precipitated or was associated with oxidized Fe(III) as mixed Fe(II)-Fe(III) nanoparticles, which was responsible for its highest reactivity towards nitrate reduction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Intern Poster Session

This poster has been developed for display during the 2023 Intern Poster Session. The poster is apart of the Nuclear Research and Experiments category. The focus of this poster is on the modifications made to the design of an integral effect test (IET) facility currently being designed for a new Small Modular Reactor (SMR) design. My contributions made to the IET facility are laid out along with an explanation on some of the aspects of designing a new nuclear reactor. This poster covers the ideas and importance of scaling and IET facilities with the context of the standards set by the NRC. There are also graphics of some other examples of IET facilities developed for other reactor designs. My contributions include designing the piping and instrumentation layout of the IET facility using CAD software. This is a key step in the process of designing this IET facility and needs to be designed to avoid excessive head loss.

42 ENGINEERING↗

Revisiting the inelastic electron tunneling spectroscopy of single hydrogen atom adsorbed on the Cu(100) surface

Inelastic electron tunneling spectroscopy (IETS) of a single hydrogen atom on the Cu(100) surface in a scanning tunneling microscopy (STM) configuration has been investigated by employing the non-equilibrium Green’s function formalism combined with density functional theory. The electron-vibration interaction is treated at the level of lowest order expansion. Our calculations show that the single peak observed in the previous STM-IETS experiments is dominated by the perpendicular mode of the adsorbed H atom, while the parallel one only makes a negligible contribution even when the STM tip is laterally displaced from the top position of the H atom. This propensity of the IETS is deeply rooted in the symmetry of the vibrational modes and the characteristics of the conduction channel of the Cu-H-Cu tunneling junction, which is mainly composed of the 4s and 4p{sub z} atomic orbitals of the Cu apex atom and the 1s orbital of the adsorbed H atom. These findings are helpful for deepening our understanding of the propensity rules for IETS and promoting IETS as a more popular spectroscopic tool for molecular devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Interfacial electron transfer of perylenes: Influence of the anchor binding mode

Interfacial electron transfer (IET) through saturated single-linker and dual-linker groups from a perylene chromophore into nanostructured TiO2 films was studied by ultrafast spectroscopy. Perylene chromophores with one and two propanoic acid linker groups in the peri and ortho positions were investigated. In comparison to previously studied perylenes bound via unsaturated acrylic acid linkers, the chromophores with saturated linkers showed bi-exponential IET dynamics. Two distinct transfer times were observed that indicate the presence of two concurrent binding modes. A comparison between ortho- and peri-substituted sensitizers resulted in slower IET dynamics and weaker electronic coupling for ortho substitution. Finally, IET from sensitizers with saturated linker groups is neither promoted nor hindered by a second linker group. This indicates that only one of the two linkers binds covalently to the surface. This study reveals the importance of the anchor-binding mode and design considerations of the linker for regulating IET.

Chemistry↗

Integral and Separate Effects Tests for Thermal Hydraulics Code Validation for Liquid-Salt Cooled Nuclear Reactors

The objective of the 3-year project was to collect integral effects test (IET) data to validate the RELAP5-3D code and other thermal hydraulics codes for use in predicting the transient thermal hydraulics response of liquid salt cooled reactor systems, including integral transient response for forced and natural circulation operation. The reference system for the project is a modular, 900-MWth Pebble Bed Advanced High Temperature Reactor (PB-AHTR), a specific type of Fluoride salt-cooled High temperature Reactor (FHR). Two experimental facilities were developed for thermal-hydraulic integral effects tests (IETs) and separate effects tests (SETs). The facilities use simulant fluids for the liquid fluoride salts, with very little distortion to the heat transfer and fluid dynamics behavior. The CIET Test Bay facility was designed, built, and operated. IET data for steady state and transient natural circulation was collected. SET data for convective heat transfer in pebble beds and straight channel geometries was collected. The facility continues to be operational and will be used for future experiments, and for component development. The CIET 2 facility is larger in scope, and its construction and operation has a longer timeline than the duration of this grant. The design for the CIET 2 facility has drawn heavily on the experience and data collected on the CIET Test Bay, and it was completed in parallel with operation of the CIET Test Bay. CIET 2 will demonstrate start-up and shut-down transients and control logic, in addition to LOFC and LOHS transients, and buoyant shut down rod operation during transients. Design of the CIET 2 Facility is complete, and engineering drawings have been submitted to an external vendor for outsourced quality controlled construction. CIET 2 construction and operation continue under another NEUP grant. IET data from both CIET facilities is to be used for validation of system codes used for FHR modeling, such as RELAP5-3D. A set of numerical models were developed in parallel to the experimental work. RELAP5-3D models were developed for the salt-cooled PB-AHTR, and for the simulat fluid CIET natural circulation experimental loop. These models are to be validated by the data collected from CIET. COMSOL finite element models were used to predict the temperature and fluid flow distribution in the annular pebble bed core; they were instrumental for design of SETs, and they can be used for code-to-code comparisons with RELAP5-3D. A number of other small SETs, and numerical models were constructed, as needed, in support of this work. The experiments were designed, constructed and performed to meet CAES quality assurance requirements for test planning, implementation, and documentation; equipment calibration and documentation, procurement document control; training and personnel qualification; analysis/modeling software verification and validation; data acquisition/collection and analysis; and peer review.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Investigation of inelastic electron tunneling spectra of metal-molecule-metal junctions fabricated using direct metal transfer method

We measured the inelastic electron tunneling spectroscopy (IETS) characteristics of metal-molecule-metal junctions made with alkanethiolate self-assembled monolayers. The molecular junctions were fabricated using a direct metal transfer method, which we previously reported for high-yield metal-molecule-metal junctions. The measured IETS data could be assigned to molecular vibration modes that were determined by the chemical structure of the molecules. We also observed discrepancies and device-to-device variations in the IETS data that possibly originate from defects in the molecular junctions and insulating walls introduced during the fabrication process and from the junction structure.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Mechanically induced intramolecular electron transfer in a mixed-valence molecular shuttle

The kinetics and thermodynamics of intramolecular electron transfer (IET) can be subjected to redox control in a bistable [2]rotaxane comprised of a dumbbell component containing an electron-rich 1,5-dioxynaphthalene (DNP) unit and an electron-poor phenylene-bridged bipyridinium (P-BIPY2+) unit and a cyclobis (paraquat-p-phenylene) (CBPQT4+) ring component. The [2]rotaxane exists in the ground-state co-conformation (GSCC) wherein the CBPQT4+ ring encircles the DNP unit. Reduction of the CBPQT4+ leads to the CBPQT2(•+) diradical dication while the P-BIPY2+ unit is reduced to its P-BIPY•+ radical cation. A radical-state co-conformation (RSCC) results from movement of the CBPQT2(•+) ring along the dumbbell to surround the P-BIPY•+ unit. This shuttling event induces IET to occur between the pyridinium redox centers of the P-BIPY•+ unit, a property which is absent between these redox centers in the free dumbbell and in the 1:1 complex formed between the CBPQT2(•+) ring and the radical cation of methyl-phenylene-viologen (MPV•+). Using electron paramagnetic resonance (EPR) spectroscopy, the process of IET was investigated by monitoring the line broadening at varying temperatures and determining the rate constant (kET = 1.33 × 107 s-1) and activation energy (ΔG‡ = 1.01 kcal mol-1) for electron transfer. These values were compared to the corresponding values predicted, using the optical absorption spectra and Marcus–Hush theory.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tip-induced local strain on Mo S 2 / graphite detected by inelastic electron tunneling spectroscopy

We report the detection of tip-induced local strain applied to the monolayer MoS 2 grown on a graphite substrate by scanning tunneling microscope. Monolayer MoS 2 behaves as both mechanical and tunneling barriers that prevent the tip from contacting the graphite while maintaining the tunneling current. Inelastic tunneling electron spectroscopy (IETS) is utilized to probe the phonon modes in graphite. As the tip pushes the sample, IETS reveals a continuous phonon softening in graphite, corroborated by a downward shift of the phonon energy as calculated by density-functional theory. Finally, our results demonstrate a way to apply local mechanical strain and simultaneously detect the induced change in phonon modes by unitizing IETS with two-dimensional materials as a tunneling barrier.

36 MATERIALS SCIENCE↗

Resolving domain positions of cellobiose dehydrogenase by small angle X–ray scattering

The interdomain electron transfer (IET) between the catalytic flavodehydrogenase domain and the electron-transferring cytochrome domain of cellobiose dehydrogenase (CDH) plays an essential role in biocatalysis, biosensors and biofuel cells, as well as in its natural function as an auxiliary enzyme of lytic polysaccharide monooxygenase. We investigated the mobility of the cytochrome and dehydrogenase domains of CDH, which is hypothesised to limit IET in solution by small angle X-ray scattering (SAXS). CDH from Myriococcum thermophilum (syn. Crassicarpon hotsonii, syn. Thermothelomyces myriococcoides) was probed by SAXS to study the CDH mobility at different pH and in the presence of divalent cations. By comparison of the experimental SAXS data, using pair-distance distribution functions and Kratky plots, we show an increase in CDH mobility at higher pH, indicating alterations of domain mobility. To further visualise CDH movement in solution, we performed SAXS-based multistate modelling. Glycan structures present on CDH partially masked the resulting SAXS shapes, we diminished these effects by deglycosylation and studied the effect of glycoforms by modelling. The modelling shows that with increasing pH, the cytochrome domain adopts a more flexible state with significant separation from the dehydrogenase domain. On the contrary, the presence of calcium ions decreases the mobility of the cytochrome domain. Experimental SAXS data, multistate modelling and previously reported kinetic data show how pH and divalent ions impact the closed state necessary for the IET governed by the movement of the CDH cytochrome domain.

59 BASIC BIOLOGICAL SCIENCES↗

Validation Data Acquisition in HTTF during PCC Events

A validation experimental campaign was conducted in an Integral Effect Test (IET) facility of High Temperature Gas Reactors (HTGR), the High-Temperature Test Facility (HTTF) at Oregon State University (OSU). The HTTF simulates Depressurized and Pressurized Conduction Cooldowns (DCC and PCC). This campaign required the development of a new laser spectroscopic diagnostic to measure velocity in the challenging conditions of the HTTF: low speed (~1 m/s) gas flows at HTGR prototypical temperature and 1/10th pressure. This was a collaborative effort between co-PIs at The George Washington University (GW), Oregon State University (OSU), and NASA Langley Research Center. The main accomplishments of this project include the record for dynamic range for velocimetry, highest accuracy obtained with this technique, successful deployment in an IET leading to new validation matrix for CFD. These are detailed below and in manuscript appended to this executive summary. For this project, we introduced a new class of laser spectroscopic diagnostics to Thermal-Hydraulics to measure velocity of gases; furthermore, the diagnostic was demonstrated in-situ in an IET during DCC events. In such scenarios, particles used in mainstream techniques, like Particle Image Velocimetry (PIV) are not appropriate as they settle down too rapidly and also contaminate the experimental facility. Molecular tracers stay mixed within the working gas and can seed the flow in a technique called Molecular Tagging Velocimetry (MTV). In MTV a molecular tracer is photo-dissociated by a first (write) laser into radicals or molecules. The pattern created by the write laser is then interrogated with planar laser-induced fluorescence (PLIF), the read pulse(s), which are recorded with a camera. The pattern is probed and matched at two times (interval or probe time, dt), resulting in a time-of-flight velocimetry technique. This project demonstrated a new application range for MTV in gases. MTV has been extensively used for high-speed gas dynamics: molecules do not suffer from inertia associated with particles in regions of high accelerations (such as shock waves). For high-speed flows, the probe time is on the order of 0.1-10 µs. In time-of-flight techniques, the velocity is reconstructed from the recorded displacement, dx, between time interval dt: U = dx/dt. To first order, the resolution of the pattern matching is typically a (fixed) fraction of a pixel; therefore the resolution of the velocity measurement increases with dx and, for a given flow velocity, dt. For the low-speed flows of interest here, this requires long probe time, and therefore finding tracers that are stable for a long time. After an extensive literature survey we identified 6 tracers that would be suitable. We also worked with Spectra Physics to design a custom laser system that is flexible enough to probe these various tracers. The final instrument is made of 4 lasers that are integrated into a compact and movable cart to facilitate the deployment of the instrument off-site. One unique aspect of the laser system is the tunable dye laser (needed to do PLIF of the radicals). By being pumped by two Nd:YAG lasers, this laser is able to provide two pulses with any probe time (dt) for wavelengths between 200 and 900 nm with a linewidth of 3 pm. Accommodating the dual-pulse capability required customizing the pump lasers and the dye laser, making this system unique. Additionally, a custom UV-intensified CCD camera capable of frame-straddling and exposure time as short as 10 ns was acquired. More than two-third of the instrument cost (~$200k) was covered by a cost sharing from the PI’s startup funds. Of the 6 potential tracers identified, two were tested extensively (H2O and N2O) at high-temperature and elevated pressure at GW prior to conducting the tests at OSU. For both tracers, an Ar-F laser (193 nm, 10 ns, 10 mJ/pulse) photo-dissociates trace amounts (0.1 – 5% molar fraction) of the gases into OH and NO. OH is probed at 281.905 nm and NO at 226.186 nm (4-30mJ, 10 ns pulse). NO is very stable in inert environment and we could reconstruct velocities precisely with probe delay times as long at 40 ms, compared to 2 ms for OH, resulting in increased precision. Therefore, for the tests in the HTTF, N2O was selected as the final tracer and its optimal concentration was determined to be 0.5% molar. In the GW laboratory, we obtained a velocity measurement precision of 4 mm/s at conditions mimicking the HTTF tests. We also demonstrated the benefit of molecular tracers over particles and the flexibility of our instrument by continuously measuring velocity from 1000 to 0.1 m/s in a blow down test. This represents a dynamic range on velocity of 80 dB, which is unprecedented for velocimetry! Once the diagnostic was optimized, two two-week campaigns were conducted in the HTTF. This experimental campaign required numerous practical solutions to successfully and rapidly deploy this very sensitive table-top diagnostic in-situ. This was accomplished thanks to very extensive planning from all parties involved in the project. Due to constraints on availability of the HTTF, only adiabatic DCC tests were conducted. Specifically, the velocity was measured at the exit of the hot leg into the Reactor Cavity Simulation Tank (RCST). We were able to record the gas velocity associated with the air ingress for long times (up to one hour). Depending on the initial conditions (density of the gases in the Reactor Pressure Vessel and the RCST) the lock exchange lasted 30-60 s past the valve openings. Large vortices were identified within the shear layer at the interface of the cross flow. These vortices are an indication of shear-driven instability between the counter streams of different density. After the lock-exchange, a small residual flow was still present and its strength decayed exponentially. It finds its source in a buoyancy difference between the gases in both vessels due to the mixing and diffusion of the gases in the cross-over duct and the RPV lower plenum. We did not expect to capture this part of the transient, which would have been less significant (if not negligible) in the presence of a heated core; the precision of our measurement in the HTTF was 6 mm/s, which exceeded our expectations for such a complex test! Using commercial software (Fluent) we simulated the experiment with Computational Fluid Dynamic (CFD) using Reynolds Averaged Navier-Stokes (RANS) turbulence models. We were not able to accurately reproduce the shear layer instability, mixing, and diffusion captured in our experimental data, even with large 3D meshes (>10 M points). We attributed this to the inadequacy of the RANS models for the flow of interest: our experimental Reynolds number was too low and was outside the applicability range of the RANS models. Instead, we should have employed CFD with less modeling, such as Large Eddy (LES) or even Direct Numerical (DNS) simulations. Unfortunately, we did not have the computational resources to do so. Finally, it should be noted that this experimental technique holds great promises for measuring velocity in thermalhydraulics. MTV has an application domain (highlighted in the narrative) that is complimentary to more established (and simpler) techniques, such as PIV. It has attracted the attention of several thermalhydraulics researchers and sponsors to measure velocity in harsh environments. The spectroscopic nature of this technique also enables to expand it to measure temperature and concentration simultaneously to velocity. In lieu of a narrative, 4 detailed journal publications are appended to this executive summary to describe the various development and accomplishments during this project. They include 2 published manuscripts (Experiments in Fluids and Measurement Science and Technology), and two invited contributions following the NURETH-17 conference (Nuclear Science and Technology). Our current Nuclear Engineering and Design draft is not included at this time.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Major results from safety-related integral effect tests with VISTA-ITL for the SMART design

A series of integral effect tests (IETs) was performed by the Korea Atomic Energy Research Inst. (KAERI) using the VISTA integral test loop (VISTA-ITL) as a small-scale IET program. Among them this paper presents major results acquired from the safety-related IETs with the VISTA-ITL facility for the SMART design. Three small-break loss-of-coolant accident (SBLOCA) tests of safety injection system (SIS) line break, shutdown cooling system (SCS) line break and pressurizer safety valve (PSV) line break were successfully performed and the transient characteristics of a complete loss of flowrate (CLOF) was simulated properly with the VISTA-ITL facility. (authors)

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Scaling for Nuclear Reactor System: Overview

A scaling analysis is essential for predicting the behavior of a reactor system under various operating conditions, as well as for ensuring safe and reliable experimentation and adequate dataset generation for supporting the system code model development and assessment in accordance with USNRC guidelines 1.203. Testing and modeling can be carried out at various scales, from small test units to full-scale reactors, to validate the predictions produced by the analysis. However, due to the cost and challenges associated with full-scale testing, the nuclear industry uses scaled test facilities—integral effect test (IET) and separate effect test (SET)—to identify potential design issues and optimize the design to ensure regulatory compliance for safer operation and anticipated accident management. In general, IET facilities are non-nuclear thermal hydraulics test facilities. In contrast, SET facilities can be non-nuclear testing (e.g., steam generator, containment, pump system SETs) and nuclear testing (mostly fuel-material irradiation testing). IETs are used to study the system-level thermal-hydraulic behavior of the reactor coolant system (RCS) under different anticipated operational occurrences (AOOs) and design basis accidents (DBAs) such as loss-of-coolant-accident (LOCA) and loss-of-power (i.e., station blackout) and loss-of-flow (i.e., failure of RCS pump). Several LOCA scenarios could happen in reactor DBAs, such as main steam line break (MSLB), SG tube rapture (SGTR), break in direct vessel injection (DVI), and other small breaks LOCA. Scaling analysis determines the appropriate size and operating conditions for the test facility. This involves analyzing the system's thermal-hydraulic behavior at different scales and identifying the key parameters that affect the thermal-hydraulic behavior of the reactor. These key parameters can be identified so that the scaled facility can replicate the expected conditions in a prototypical setting. The scaled facility can simulate the same flow rates, pressure gradients, heat transfer coefficients, and fluid properties as the prototype. Scaling analysis is used to ensure that the results from these tests can be scaled up to predict the behavior of a full-scale prototype with an acceptable range of scaling distortions.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Effect of MgO on Crystallization and Heat Transfer of Fluoride-Free Mold Fluxes

The effect of MgO on crystallization and heat transfer of fluoride-free mold fluxes was studied using single/double-hot thermocouple technique (SHTT/DHTT) and infrared emitter technique (IET), respectively. SHTT experiments demonstrated that the increase of MgO concentration promoted the crystallization tendency of mold fluxes. XRD analysis showed that the dominant phases changed from CaSiO{sub 3} to CaSiO{sub 3}/Ca{sub 2}MgSi{sub 2}O{sub 7}/Ca{sub 11}Si{sub 4}B{sub 2}O{sub 22}, and to Ca{sub 2}MgSi{sub 2}O{sub 7} as the MgO content was increased. The heat flux across mold flux disks was reduced from 671 to 615 kW/m{sup 2} in IET experiments when MgO concentration was increased from 0.9 to 4.9 mass pct.

36 MATERIALS SCIENCE↗

Effects of particle size and AQDS on the flow of electron equivalents between magnetite and aqueous Fe2+

Magnetite can occur naturally in nano- to micro-size regimes and widely coexists with aqueous Fe2+ (Fe2+ (aq)) in natural environments. However, the effects of magnetite particle size on its interaction with Fe2+ (aq) in anoxic subsurface environments, particularly with redox-active organics, remain unclear. In this study, the interactions of Fe2+ (aq) with magnetite particles of 12 nm versus 109 nm (Mag-12 vs. Mag-109), with/without anthraquinone- 2,6-disulfonate (AQDS), were studied based on equilibrium Fe2+ (aq) concentrations, kinetics of AQDS reduction, and structural versus surface-localized Fe(II)/Fe(III) ratios (xstru and xsurf) of magnetite. In the absence of AQDS, Mag-12 tends to release Fe2+ (aq) at pH 7 but sorb Fe2+ (aq) at pH 8, while Fe2+ (aq) uptake by Mag-109 is observed at both pH 7 and 8. The amounts of Fe2+ (aq) adsorbed per unit area of Mag-109 is higher than that of Mag-12, due to the higher electron-accepting capacity of Mag-109 that facilitates interfacial electron transfer (IET) from surfaceassociated Fe(II) to structural Fe(III). The increases of xstru and xsurf in Mag-109 after reaction with Fe2+ (aq) at pH 7 and 8 suggest Fe2+ (aq) incorporation or electron injection into the structure of Mag-109. The presence of AQDS promotes Fe2+ (aq) uptake by both Mag-12 and Mag-109. However, AQDS reduction by Fe2+-amended Mag-12 results in the decrease of xstru and inhibits Fe2+ (aq) incorporation or electron injection into the structure. On the contrary, the increase of xstru observed in Fe2+-amended Mag-109 after reaction with AQDS suggests that Fe2+ (aq) incorporation or electron injection into the surface structure and then consequently into the interiors is more favorable for magnetite with larger particle sizes. The different flow directions of electron equivalents across the solid-solution interfaces can be attributed to the relatively higher electron-accepting capacity, i.e. redox potential, of Mag-109 than Mag-12; larger particle sizes facilitate IET from surface-associated Fe(II) to structural Fe(III) and promotes further Fe2+ (aq) uptake, culminating in the pronounced changes of redox potentials in magnetitebearing solutions. The results demonstrate that particle size and redox-active organics are important factors to affect reductive activity of Fe2+-magnetite system in redox-oscillating environments.

Peng, Huan↗