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At least 73 records · Page 4

Porous membrane enabled mass spectrometry characterization of microfluidic devices

A system for sampling a liquid includes a sample fluid conduit including a membrane having pores. The membrane prevents the passage of the sample liquid through the pores at a first pressure of the sample liquid in the sample fluid conduit. A surface sampling capture probe has a distal end. The capture probe includes a solvent supply conduit and a solvent exhaust conduit. A solvent composition flowing at the distal end of the capture probe establishes a liquid junction with the membrane and establishes a second pressure within the liquid junction at the membrane. The second pressure is lower than the first pressure. Sample liquid will be drawn through the pores of the membrane by the second pressure at the liquid junction. A method for sampling a liquid and for performing chemical analysis on a liquid are also disclosed.

Cahill, John F.↗

Characterization of Tank 11H Samples from Tank Closure Cesium Removal 1A (TCCR 1A) Batch 1

Savannah River Mission Completion (SRMC) is currently operating the Tank Closure Cesium Removal 1A (TCCR 1A) process to remove 137 Cs from tank waste supernate using an ion exchange process. The TCCR 1A unit processes dissolved salt fed from Tank 10H through a series of ion exchange columns containing crystalline silicotitanate (CST, IONSIV TM R9120-B, 30x60) and the effluent is then discharged to Tank 11H. In support of the TCCR 1A program, SRNL analyzed samples taken from Tank 11H (without tank mixing) before, during, and at the completion of TCCR 1A Batch 1 processing. Tank 11H serves as the receipt tank for the filtered and cesium removed product from the TCCR 1A system. Processing of Batch 1 commenced on January 13, 2022 and completed on February 17, 2022, after processing approximately 70,100 gallons. A pre-production sample was collected from the heel remaining in Tank 11H just before Batch 1 processing began. In addition, five interim surface samples were collected from Tank 11H during processing, and both a surface and a variable depth sample (VDS, ~7” from tank bottom) were collected just after processing completed. Analysis of all samples included density and gamma spectroscopy, in addition to a more comprehensive suite of analytes for the pre- and post-production samples. The density of the pre-production sample was the highest of all samples measured and was then observed to decrease for the first two interim samples, followed by becoming fairly consistent for the remainder of the samples (~1.3 g/mL). The density of 1.3 g/mL is similar to the density measured for one of the three Tank 10H qualification samples (HTF-10-21-126). The 137 Cs activity was found to decrease as additional decontaminated effluent from the TCCR columns was added to Tank 11H during processing; however, an increase in activity was observed during periods of no processing which can be attributed to leaching of 137 Cs from the known solids in Tank 11H. The Cs isotope concentrations in the Tank 11H postproduction surface sample were determined to be 99.7-99.8% lower than the concentrations measured in the Tank 10H feed as measured by mass spectrometry.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Plasma-arc lamp high heat flux cycling exposure of neutron irradiated tungsten materials

Thick plate, unalloyed W was neutron irradiated in the High Flux Isotope Reactor (HFIR) at 550 °C to a fast fluence of 1.24 × 10 25 n m -2 E > 0.1 MeV (~0.24 dpa). Unirradiated and irradiated specimens of the material were high heat flux (HHF) tested in the Plasma Arc Lamp (PAL) facility. The PAL uses a high-power photon source to provide a broad and even heat distribution on the sample surface. To simulate on/off cycling of normal operating plasma, the samples were exposed to approximately 800 cycles at 4.73 MW m -2 absorbed heat flux (incident heat fluxes of 10.95 MW m -2 ). Additionally, after PAL exposure, slight changes were observed on the surfaces of the samples with SEM. The samples showed some annealing in the near surface polished region, but they were all below the damage threshold for cracking or other destructive features. The PAL has a large parameter space for future testing. The use of the HFIR and PAL to sequentially expose neutron irradiated samples to HHF will be a powerful tool for understanding materials behavior in a fusion-like environment.

36 MATERIALS SCIENCE↗

Corrosion characteristics of Mo and TZM alloy for plasma facing components in molten lithium at 623 K

Here, in this study, the corrosion behaviours of molybdenum (Mo) and a Mo-based alloy (TZM) were investigated using a static immersion corrosion technique. Weight loss, surface microstructure, and corrosion depth of Mo and the TZM alloy were correlated with elements. The compatibility of Mo and the TZM alloy in static liquid Li was suitable. Mo demonstrated uniform corrosion with a homogenous dissolution of free C and Mo, and TZM alloy exhibited a nonuniform corrosion behaviour with a preferential grain boundary attack caused by the selective dissolution of free C, Ti, and Zr. When the surface oxidation layer of the samples was consumed, free C from Mo and TZM diffused into molten Li to form Li 2 C 2 and then was captured by Zr, Ti, and Mo to form thermodynamically stable carbides, which resulted in the enrichment of the C layer near the sample surfaces. In addition, Ti and Zr acted as N-trappers in liquid Li; the formation of Zr and Ti nitrides resulted in the enrichment of N, Ti, and Zr elements on the surface and led to TZM corrosion increase. Thus, Zr and Ti depletion, pitting, and grain boundary corrosion were problematic for TZM under long-term exposure to liquid Li. Reducing the content of free C and nonmetallic N and increasing the amount of Ti and Zr carbides on the surface of and inside the raw TZM alloy helped improve the corrosion resistance of TZM in liquid Li.

36 MATERIALS SCIENCE↗

Plasma Facing Component Characterization and Correlation With Plasma Conditions in Lithium Tokamak Experiment-β

Lithium coatings in the Lithium Tokamak eXperiment (LTX) led to flat temperature profiles. The flat temperature profiles were observed along with a hot, low density edge, implying a broad, collisionless scrape-off layer (SOL). Additionally, in vacuo X-ray photoelectron spectroscopy (XPS) measurements established that lithium coatings evaporatively deposited onto high-Z plasma facing components (PFCs) became oxidized while retaining the ability to achieve good plasma performance long after lithium was applied to the PFCs. Longstanding theory predicted flat temperature profiles with low recycling walls, which was presumed to be due to hydrogen binding with elemental lithium to form lithium hydride. The presence of oxidized lithium, however, raised questions regarding the exact mechanism of hydrogen retention in LTX. To investigate these questions, the upgraded facility LTX- β includes a new sample exposure probe (SEP) for more detailed in vacuo analysis of PFC samples. The SEP is equipped with a vacuum suitcase capable of transporting samples representative of the LTX- β outer midplane PFCs to a stand-alone XPS system while maintaining pressures lower than the LTX- β base vacuum to limit the contamination between sample exposure and analysis. The low-energy resolution XPS system used in past experiments could only enable the determination of elemental percentages on the PFC sample surfaces. Because the new XPS system has higher energy resolution, it is more direct to assign chemical compounds to the measured binding energies. This capability has been confirmed by comparing XPS data from PFC test samples with measurements using a commercial high-resolution XPS system. Quartz crystal microbalances (QCMs) were used to quantify the thickness of the deposited lithium on the LTX- β PFCs. This article describes the application of the SEP to characterize the PFC surfaces using XPS and their relationship to plasma conditions.

Maan, Anurag↗

Fast imaging of laser ablation of cerium: Dependence of plasma plume dynamics and structure on native oxide growth

We have imaged the evolution of plasma following nanosecond pulsed laser ablation of cerium in air with sub-10 ns resolution. We find the ablated plasma plume expansion and shape to be strongly dependent on the time after mechanical polishing of the sample surface. After an initial shock front common to both new and aged samples (velocities up to 16 km s ₋1 ), we observe a second front that is relatively localized to the surface vicinity of newly polished samples, but in the case of older samples it moves outward at velocities of up to 4 km s ₋1 . We attribute this behavior to the formation and growth of a native oxide layer on the order of hours after polishing. These results demonstrate that plasma imaging can be used to diagnose the presence of, and evaluate the extent of, thin surface oxides or other compounds that form soon after exposure to some atmosphere. These findings also highlight the need to explicitly consider the presence of such overlayers when modeling laser/metal interaction, when making measurements of vapor phase chemistry, and when analyzing the composition, phase, and morphology of solid particulates formed after the ablation of reactive metals.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

In-line measurements of below-the-surface food deformation during drying with an interference-based optical fiber strain sensor

Real-time measurements of food deformation are important for quality control in drying, yet they pose significant challenges. In this study, we developed an interference-based optical fiber strain sensor to enable in-line, continuous, below-the-surface strain measurements in drying of soft food samples. Compared to a strain resolution of 8 × 10 -4 at zero strain and 7.2 × 10 -3 at 0.20 strain reported in our previously published work, the present study achieves markedly improved resolutions of 1.3 × 10 -4 at zero strain and 7.8 × 10 -4 at 0.25 strain, which strains are the lower and higher boundaries of the dynamic range, respectively. This nearly order-of-magnitude improvement is attributed to the unique interference-based sensing mechanism, no need for calibration to convert optical signals to strain, and the system-design-enabled immunity to fiber-disk misalignments and light source intensity fluctuations. To demonstrate the in-line process monitoring, deformation measurements of fresh banana slices and sugar cookie doughs were carried out in a benchtop oven and an industrial-scale hot-air pilot dryer, respectively. In both dryers, strain measurements were continuously measured during the whole drying process at various depths and radii below the sample surfaces, with the strains up to 25%. Computer vision was used only in the benchtop drying to confirm the faithfulness of the fiber sensor measurements and cannot provide below-the-surface measurements. The measured spatiotemporal deformation allowed us to confirm the shell-hardening effect and to determine the speed and location of large deformation changes in the whole drying process, the latter of which is related to the sample cracking. To the best of the authors’ knowledge, this study is the first to report on an interferometry-based fiber sensor to measure food deformation. This sensor and the sensing mechanism have high potential for real-time process monitoring and control to prevent over-drying or cracking during drying processes.

47 OTHER INSTRUMENTATION↗

Evaluation of a high-throughput method for processing sponge-stick samples to detect viable, non-spore-forming biothreat agents

After a bioterrorism incident, surface sampling is often used to determine the extent of contamination and exposure, guiding decontamination efforts and decisions for re-occupancy of affected sites. The sponge-stick (SS) is a preferred and commonly used device for sample collection to detect both spore-forming and non-spore-forming biothreat agents from non-porous surfaces. Here, in this study, a recently developed high-throughput method (HTM) for processing SS samples to detect viable Bacillus anthracis spores was adapted for detection of non-spore-forming biothreat agents, Yersinia pestis and Francisella tularensis. The scalable HTM was used to process up to 20 SS samples simultaneously, compared to the current stomacher-based method which processes one SS at a time. Comparisons of the HTM and the stomacher-based method were statistically indistinguishable for most experiments (P > 0.05) with HTM recoveries of 37–60 % for Y. pestis inoculated at 102–103 cells/SS and held 48 h at 4 °C to mimic sample transport/storage. The HTM was integrated with Rapid Viability-Polymerase Chain Reaction (RV-PCR) analysis to detect viable Y. pestis in the presence of particulate contamination (Arizona Test Dust, ATD). This approach detected Y. pestis inoculated at 20 cells/SS and ATD did not impact detection (P > 0.05). F. tularensis showed significantly lower recoveries between no-hold time and 48-h hold time (4 °C, P < 0.05) using the HTM, which further testing showed could be due to toxicity of the neutralizing buffer used for SS pre-wetting. With modifications, this method could enhance throughput capacity while maintaining similar recovery efficiencies to current methods for other non-spore-forming bacterial pathogens.

Biological and medical sciences↗

The right conditions for high-precision dynamic temperature and heat capacity measurement via pyrometry and conductivity

The pursuit of accurate bulk temperature T under extreme conditions has been a long-standing goal of the high pressure science community, complicated by a lack of data to inform models. To reach these extremely high-pressure, high-temperature (high P − T) conditions, a combination of dynamic and heated static experiments (e.g., diamond or gem anvil cel experiments) are used. For example, in a diamond anvil cell (DAC) experiment, a sample placed in the DAC is first pressurized. Following pressurization, the sample T is increased either by heating the entire DAC (usually using resistive heating, and limited to ∼1000K) or by applying intense laser power to the sample surfaces. In a dynamic experiment, the process of pressurizing the sample also heats it. In the case of shock physics experiments, such heating is substantial, easily reaching thousands of Kelvin; in our work we have seen T ∼17000K. Most methods of measuring temperature at ambient are not compatible with experiments under these high-pressure, high-temperature conditions: thermocouples break, melt, or have conductivity properties that differ from ambient where they are calibrated; thermometers would melt; both are too slow. As a result most methods are based on non-contact techniques such as x-ray diffraction broadening, neutron scattering, or optical methods. Of these, optical methods using the visible and near-infrared region of the spectrum are the most commonly used as the sources and detectors are readily available. In the case of optical methods the optical depth, and therefore the measurement location, is limited to the surface. When a window or anvil material is used, heat flows from the sample into the window/anvil. Likewise, if the sample undergoes a change in thermodynamic state, such as expansion upon release, different T may be expected. As a result, the surface or apparent temperature T app measurement will differ from the bulk or interior temperature that is desired. This surface measurement must be related to the bulk measurement using thermal transport models and material models. While it is tempting to conclude that one should just use x-ray methods that directly probe the interior, even these methods have been shown to depend on thermal transport and material models. Regardless of the method used to create the high P − T condition, therefore, we must understand the role of thermal transport and material models upon our interpretation of the T measurement, as well as the errors and uncertainties associated with the choice of models used in the analysis. This is a substantial area of research and this paper is by no means a complete survey of the relevant sources of uncertainty. For example, we have yet to begin to address alternate transport models in a detailed manner (e.g., Tan-Ahrens), or the many models that use additional layers to approximate melting, turbulence, or epitaxial phenomena). Likewise, we have not explored the impact upon uncertainty of thermal models that use temperature-dependent thermal transport coefficients, or the wide range of material models that can be applied. Instead, this paper focuses on using one simple model, the Urtiew-Grover model, to understand the sources of error in T measurement so that we may identify how best to focus future research efforts to return the best improvements and avoid working on over-optimizing a single type of measurement. To this end, we work through some of the best and worst case scenarios for T measurement.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Preliminary Test Design and Plan for a Canister Deposition Field Demonstration

This report provides a high-level test plan for deploying three commercial 32PTH2 spent nuclear fuel (SNF) canisters inside NUHOMS Advanced Horizontal Storage Modules (AHSM) from Orano (formerly Transnuclear Inc.). The details contained in this report represent the best designs and approaches explored for testing as of this publication. Given the rapidly developing nature of this test program, some of these plans may change to accommodate new objectives or adapt in response to conflicting requirements. The goal of the testing is to collect highly defensible and detailed surface deposition measurements from the surface of dry storage systems in a marine coastal environment to guide chloride-induced stress corrosion crack (CISCC) research. To facilitate surface sampling, the otherwise highly prototypic dry storage systems will not contain SNF but rather will be electrically heated to mimic the thermal-hydraulic environment. Instrumentation throughout the canister, storage module, and environment will provide an extensive amount of information for the use of model validation. Manual sampling over a comprehensive portion of the canister surface at regular time intervals will offer a high-fidelity quantification of the conditions experienced in a harsh yet realistic environment.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Status Update for the Canister Deposition Field Demonstration

This report updates the high-level test plan for evaluating surface deposition on three commercial 32PTH2 spent nuclear fuel (SNF) canisters inside NUTECH Horizontal Modular Storage (NUHOMS) Advanced Horizontal Storage Modules (AHSM) from Orano (formerly Transnuclear Inc.) and provides a description of the surface characterization activities that have been conducted to date. The details contained in this report represent the best designs and approaches explored for testing as of this publication. Given the rapidly developing nature of this test program, some of these plans may change to accommodate new objectives or requirements. The goal of the testing is to collect highly defensible and detailed surface deposition measurements from the surface of dry storage canisters in a marine coastal environment to guide chloride-induced stress corrosion crack (CISCC) research. To facilitate surface sampling, the otherwise highly prototypic dry storage systems will not contain SNF but rather will be electrically heated to mimic the thermal-hydraulic-environment. Instrumentation throughout the canister, storage module, and environment will provide an extensive amount of information for the use of model validation. Manual sampling over a comprehensive portion of the canister surface at regular time intervals will offer a high-fidelity quantification of the conditions experienced in a harsh yet realistic environment.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Status Update for the Canister Deposition Field Demonstration

This report updates the high-level test plan for evaluating surface deposition on three commercial 32PTH2 spent nuclear fuel (SNF) canisters inside NUTECH Horizontal Modular Storage (NUHOMS) Advanced Horizontal Storage Modules (AHSMs) from Orano (formerly Transnuclear Inc.) and provides a description of the surface characterization activities that have been conducted to date. The details contained in this report represent the best designs and approaches explored for testing as of this publication. Given the rapidly developing nature of this test program, some of these plans may change to accommodate new objectives or requirements. The goal of the testing is to collect highly defensible and detailed dust deposition measurements from the surface of dry storage canisters in a marine coastal environment to guide chloride-induced stress corrosion crack (CISCC) research. To facilitate surface sampling, the otherwise highly prototypic dry storage systems will not contain SNF but rather will be electrically heated to mimic the decay heat and thermal hydraulic environment. Test and heater design is supported by detailed computational fluid dynamics modeling. Instrumentation throughout the canister, storage module, and environment will provide extensive information about thermal-hydraulic behavior. Manual sampling over a comprehensive portion of the canister surface at regular time intervals will offer a high-fidelity quantification of the conditions experienced in a harsh yet realistic environment. Functional testing of the finalized heater assemblies and test apparatus is set to begin in December 2022. The proposed delivery of the canisters to the host test site is June/July 2023, which is well ahead of when the AHSM installations would be completed.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Multislice forward modeling of coherent surface scattering imaging on surface and interfacial structures

To study nanostructures on substrates, surface-sensitive reflection-geometry scattering techniques such as grazing incident small angle X-ray scattering are commonly used to yield an averaged statistical structural information of the surface sample. Grazing incidence geometry can probe the absolute three-dimensional structural morphology of the sample if a highly coherent beam is used. Coherent surface scattering imaging (CSSI) is a powerful yet non-invasive technique similar to coherent X-ray diffractive imaging (CDI) but performed at small angles and grazing-incidence reflection geometry. A challenge with CSSI is that conventional CDI reconstruction techniques cannot be directly applied to CSSI because the Fourier-transform-based forward models cannot reproduce the dynamical scattering phenomenon near the critical angle of total external reflection of the substrate-supported samples. To overcome this challenge, we have developed a multislice forward model which can successfully simulate the dynamical or multi-beam scattering generated from surface structures and the underlying substrate. The forward model is also demonstrated to be able to reconstruct an elongated 3D pattern from a single shot scattering image in the CSSI geometry through fast-performing CUDA-assisted PyTorch optimization with automatic differentiation.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Analysis of solid uranium particulates on cotton swipes with an automated microextraction-ICP-MS system

Here, an automated microextraction method coupled to an inductively coupled plasma – mass spectrometer (ICP-MS) was developed for the direct analysis of solid uranium particulates on the surface of cotton swipes. The microextraction probe extracts particulates from the sample surface, in a flowing solvent, and directs the removed analyte to an ICP-MS for isotopic determination. The automated system utilizes a mechanical XY stage that is software controlled with the capability of saving and returning to specific locations and a camera focused to the swipe surface for optimal viewing of the extracted locations (i.e., material present). Here, particulates (n = 135) were extracted and measured by ICP-MS, including 35 depleted uranyl nitrate hexahydrate (UN) (used for mass bias corrections), 50 uranyl fluoride (UO 2 F 2 ), and 50 uranyl acetate (UAc) particulates. Blank extractions were performed on the cotton swipes between triplicate sample analyses. Between each swipe extraction, the probe was sent between two wells containing 10% and 5% HNO 3 to clean the probe head and to eliminate any analyte carryover between particulates. The measured 235 U/ 238 U and 234 U/ 238 U isotope ratios for the UO 2 F 2 particulates were 0.00725(8) and 0.000054(4), a percent relative difference (% RD) of –0.041% and –1.7% from the reference isotope ratios determined in-lab through multi-collector ICP-MS analysis of dissolved aliquots of the U material. The UAc samples had a measured 235 U/ 238 U isotope ratio of 0.00206(7), a –0.96% relative difference from the reference value of 0.00208(1). The 234 U/ 238 U and 236 U/ 238 U isotope ratios were 0.000008(1) and 0.000031(4), –5.1% RD and –4.3% RD, respectively. The automated sample stage enabled seamless and rapid particle analysis, leading to a significant increase in throughput versus what was previously possible. Additionally, the saved location capability reduced user sampling error as sampling locations were easily stored and recalled. Analysis of U particles on the swipe surface – including blanks, mass bias, and triplicate extractions – was completed in less than an hour without any sample preparation necessary.

47 OTHER INSTRUMENTATION↗

An in situ shearing x-ray measurement system for exploring structures and dynamics at the solid–liquid interface

Revealing interfacial structure and dynamics has been one of the essential thematic topics in material science and condensed matter physics. Synchrotron-based x-ray scattering techniques can deliver unique and insightful probing of interfacial structures and dynamics, in particular, in reflection geometries with higher surface and interfacial sensitivity than transmission geometries. We demonstrate the design and implementation of an in situ shearing x-ray measurement system, equipped with both inline parallel-plate and cone-and-plate shearing setups and operated at the advanced photon source at Argonne National Laboratory, to investigate the structures and dynamics of end-tethered polymers at the solid-liquid interface. With a precise lifting motor, a micrometer-scale gap can be produced by aligning two surfaces of a rotating upper shaft and a lower sample substrate. A torsional shear flow forms in the gap and applies tangential shear forces on the sample surface. The technical combination with nanoscale rheology and the utilization of in situ x-ray scattering allow us to gain fundamental insights into the complex dynamics in soft interfaces under shearing. In this work, we demonstrate the technical scope and experimental capability of the in situ shearing x-ray system through the measurements of charged polymers at both flat and curved interfaces upon shearing. Furthermore, through the in situ shearing x-ray scattering experiments integrated with theoretical simulations, we aim to develop a detailed understanding of the short-range molecular structure and mesoscale ionic aggregate morphology, as well as ion transport and dynamics in soft interfaces, thereby providing fundamental insight into a long-standing challenge in ionic polymer brushes with a significant technological impact.

36 MATERIALS SCIENCE↗

Copper migration and surface oxidation of CuxBi2Se3 in ambient pressure environments

Abstract Chemical modifications such as intercalation can be used to modify surface properties or to further functionalize the surface states of topological insulators (TIs). Using ambient pressure x-ray photoelectron spectroscopy, we report copper migration in C u x B i 2 S e 3 , which occurs on a timescale of hours to days after initial surface cleaving. The increase in near-surface copper proceeds along with the oxidation of the sample surface and large changes in the selenium content. These complex changes are further modeled with core-level spectroscopy simulations, which suggest a composition gradient near the surface which develops with oxygen exposure. Our results shed light on a new phenomenon that must be considered for intercalated TIs—and intercalated materials in general—that surface chemical composition can change when specimens are exposed to ambient conditions.

36 MATERIALS SCIENCE↗

Surface science insight note: A linear algebraic approach to elucidate native films on Fe 3 O 4 surface

Standard materials are often used to obtain spectra that can be compared to those from unknown samples. Spectra measured from these known substances are also used as a means of computing sensitivity factors to allow quantification by X-ray photoelectron spectroscopy (XPS) of less well-defined materials. Spectra from known materials also provide line shapes suitable for inclusion in spectral models which, when fitted to spectra, permit the chemical state for a sample to be assessed. Both types of information depend on isolating photoemission signals from the inelastically scattered signal. In this Insight note, technical issues associated with the use of XPS of as received Fe 3 O 4 powder sample surface are discussed. The Insight note is designed to show how linear algebraic techniques applied to data collected from a sample marketed as pure Fe 3 O 4 powder are used to verify that XPS has been performed on chemistry representative of the sample. The methods described in this Insight note can further be utilized in elucidating complex XPS data obtained from thin films formed or evolved during cyclic/non-steady use of complex (electro)catalyst surfaces, especially in the presence of contaminants.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Carbon-Mediated Oxygen Vacancy Creation at Hematite Interfaces

Nanoscale iron oxides (e.g., hematite (a-Fe 2 O 3 )) have unique properties, such as enhanced chemical reactivity and high surface area, when compared with their bulk counterparts. These nanoscale surfaces can be more reactive due to the presence of defects (e.g., oxygen vacancies). In this work, we probed the surface chemistry of bulk and nanoscale hematite via X-ray photoelectron spectroscopy, electron microscopy, and powder X-ray diffraction. Oxygen exposure and vacuum annealing experiments were conducted to add or remove oxygen vacancies and remove adventitious carbon. In the absence of the oxygen annealing step, vacuum annealing resulted in partial reduction of Fe(III) to Fe(II) on all hematite surfaces. This was a size-dependent effect with the extent of reduction increasing as the crystallite size decreased. In addition, the atomic concentrations of carbon increased on all iron oxide surfaces after vacuum annealing. Oxygen annealing almost completely removed carbon from sample surfaces, and no Fe(III) reduction was observed in the absence of carbon. Under these conditions, the results reveal that carbonaceous material enhances oxygen vacancy formation, which then facilitates the reduction of Fe(III) on hematite surfaces. We provide new insights into the mechanisms of Fe(III) reduction on both bulk and nanoscale hematite surfaces and establish the major role of carbon in oxygen vacancy formation.

Zengotita, Frances E. [University of Notre Dame, I↗