Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “isotopic tracers”

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.

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

At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Radiation Enhanced Anion Diffusion in Chromia

Cr 2 O 3 is a ubiquitous passivating film on alloys that is vital to their stability and performance in hostile environments. In this study, we directly observe and measure how anion transport through the oxide is affected by 400 keV Ar 2+ ion irradiation as a function of temperature (30–500 °C) and dose (0.33–2.00 dpa) in single-crystal Cr 2 O 3 films using embedded 18 O isotopic tracers and atom probe tomography. Diffusion coefficients are experimentally determined and compared to a chemical rate theory model. Experimental and theoretical results are broadly in agreement, showing anion diffusion increases by at least 4–5 orders of magnitude upon irradiation with a weak dependence on temperature and a stronger dose-driven sink-strength dependence. These results reveal that radiation could significantly reduce the protectiveness of Cr 2 O 3 films when passivity relies upon limited anion diffusivity, even at relatively modest levels of irradiation and low temperatures.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2022

Defining the Sphagnum Core Microbiome across the North American Continent Reveals a Central Role for Diazotrophic Methanotrophs in the Nitrogen and Carbon Cycles of Boreal Peatland Ecosystems

Peat mosses of the genus Sphagnum are ecosystem engineers that frequently predominate over photosynthetic production in boreal peatlands. Sphagnum spp. host diverse microbial communities capable of nitrogen fixation (diazotrophy) and methane oxidation (methanotrophy), thereby potentially supporting plant growth under severely nutrient-limited conditions. Moreover, diazotrophic methanotrophs represent a possible “missing link” between the carbon and nitrogen cycles, but the functional contributions of the Sphagnum-associated microbiome remain in question. A combination of metagenomics, metatranscriptomics, and dual-isotope incorporation assays was applied to investigate Sphagnum microbiome community composition across the North American continent and provide empirical evidence for diazotrophic methanotrophy in Sphagnum-dominated ecosystems. Remarkably consistent prokaryotic communities were detected in over 250 Sphagnum SSU rRNA libraries from peatlands across the United States (5 states, 17 bog/fen sites, 18 Sphagnum species), with 12 genera of the core microbiome comprising 60% of the relative microbial abundance. Additionally, nitrogenase (nifH) and SSU rRNA gene amplicon analysis revealed that nitrogen-fixing populations made up nearly 15% of the prokaryotic communities, predominated by Nostocales cyanobacteria and Rhizobiales methanotrophs. While cyanobacteria comprised the vast majority (>95%) of diazotrophs detected in amplicon and metagenome analyses, obligate methanotrophs of the genus Methyloferula (order Rhizobiales) accounted for one-quarter of transcribed nifH genes. Furthermore, in dual-isotope tracer experiments, members of the Rhizobiales showed substantial incorporation of 13 CH 4 and 15 N 2 isotopes into their rRNA. Our study characterizes the core Sphagnum microbiome across large spatial scales and indicates that diazotrophic methanotrophs, here defined as obligate methanotrophs of the rare biosphere (Methyloferula spp. of the Rhizobiales) that also carry out diazotrophy, play a keystone role in coupling of the carbon and nitrogen cycles in nutrient-poor peatlands.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Isotopically nonstationary metabolic flux analysis of plants: recent progress and future opportunities

Metabolic flux analysis (MFA) is a valuable tool for quantifying cellular phenotypes and to guide plant metabolic engineering. By introducing stable isotopic tracers and employing mathematical models, MFA can quantify the rates of metabolic reactions through biochemical pathways. Recent applications of isotopically nonstationary MFA (INST–MFA) to plants have elucidated nonintuitive metabolism in leaves under optimal and stress conditions, described coupled fluxes for fast–growing algae, and produced a synergistic multi–organ flux map that is a first in MFA for any biological system. Finally, these insights could not be elucidated through other approaches and show the potential of INST–MFA to correct an oversimplified understanding of plant metabolism.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Resolving Diverse Oxygen Transport Pathways Across Sr‐Doped Lanthanum Ferrite and Metal‐Perovskite Heterostructures

Abstract Perovskite structured transition metal oxides are important technological materials for catalysis and solid oxide fuel cell applications. Their functionality often depends on oxygen diffusivity and mobility through complex oxide heterostructures, which can be significantly impacted by structural and chemical modifications, such as doping. Further, when utilized within electrochemical cells, interfacial reactions with other components (e.g., Ni‐ and Cr‐based alloy electrodes and interconnects) can influence the perovskite's reactivity and ion transport, leading to complex dependencies that are difficult to control in real‐world environments. Here, this work uses isotopic tracers and atom probe tomography to directly visualize oxygen diffusion and transport pathways across perovskite and metal‐perovskite heterostructures, that is, (Ni‐Cr coated) Sr‐doped lanthanum ferrite (La 0.5 Sr 0.5 FeO 3 ; LSFO). Annealing in 18 O 2(g) results in elemental and isotopic redistributions through oxygen exchange (OE) in the LSFO while Ni‐Cr undergoes oxidation via multiple mechanisms and transport pathways. Complementary density functional theory calculations at experimental conditions provide rationale for OE reaction mechanisms and reveal a complex interplay of different thermodynamic and kinetic drivers. These results shed light on the fundamental coupling of defects and oxygen transport in an important class of catalytic materials.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Development of Chemical Procedures for Isotope Harvesting: Separation of Trace Hafnium from Tungsten

The separation of trace hafnium from bulk tungsten alloys is of interest for isotope harvesting at the National Superconducting Cyclotron Laboratory and the Facility for Rare Ion Beams because 172 Hf, the parent of 172 Lu, accumulates in tungsten alloy beam blockers at these facilities. In this work, a procedure for the separation of trace hafnium from a bulk tungsten alloy (454 g) was established using tracer isotopes ( 175 Hf, 88 Zr, 173 Lu, and 88 Y). Here, the procedure employed dissolution in an HF–HNO 3 solution followed by a calcium fluoride precipitation, and then extraction chromatography was used for more selective separation steps. Two stages of column separations using LN resin (HDEHP based) and TRU resin (CMPO based) were performed. Gamma-ray spectroscopy and mass spectrometry were used to analyze the final hafnium sample and follow the steps in the chemical processing. Furthermore, the final recovery of hafnium was high (90 ± 8)%, and the mass of tungsten and other transition metals was reduced to near background levels (as determined by ICP-MS of the blank acid solutions). Zirconium follows hafnium quantitatively in this procedure; there was no detectable 173 Lu in the final hafnium sample.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2020

Measurement Error and Resolution in Quantitative Stable Isotope Probing: Implications for Experimental Design

Quantitative stable isotope probing (qSIP) estimates isotope tracer incorporation into DNA of individual microbes and can link microbial biodiversity and biogeochemistry in complex communities. As with any quantitative estimation technique, qSIP involves measurement error, and a fuller understanding of error, precision, and statistical power benefits qSIP experimental design and data interpretation. We used several qSIP data sets—from soil and seawater microbiomes—to evaluate how variance in isotope incorporation estimates depends on organism abundance and resolution of the density fractionation scheme. We assessed statistical power for replicated qSIP studies, plus sensitivity and specificity for unreplicated designs. As a taxon’s abundance increases, the variance of its weighted mean density declines. Nine fractions appear to be a reasonable trade-off between cost and precision for most qSIP applications. Increasing the number of density fractions beyond that reduces variance, although the magnitude of this benefit declines with additional fractions. Our analysis suggests that, if a taxon has an isotope enrichment of 10 atom% excess, there is a 60% chance that this will be detected as significantly different from zero (with alpha 0.1). With five replicates, isotope enrichment of 5 atom% could be detected with power (0.6) and alpha (0.1). Finally, we illustrate the importance of internal standards, which can help to calibrate per sample conversions of %GC to mean weighted density. These results should benefit researchers designing future SIP experiments and provide a useful reference for metagenomic SIP applications where both financial and computational limitations constrain experimental scope.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Coupled feldspar dissolution and secondary mineral precipitation in batch systems: 6. Labradorite dissolution, calcite growth, and clay precipitation at 60 °C and pH 8.2–8.4

Here, we conducted experiments on concurrent labradorite dissolution, calcite precipitation, and clay precipitation in batch reactor systems and tracked reaction processes using multiple isotope tracers. Labradorite was chosen for its role as a major and reactive component in basalt; the experiments thus directly impact our understanding of CO 2 storage in basalt aquifers and enhanced rock weathering. We doped initial solutions with 29 Si, 43 Ca, and Ca 13 CO 3 (s). Experiments were conducted at 60 °C and pH ~ 8.3 for up to 840 h, with isotope ratios in the experimental aqueous solutions measured using MC-ICP-MS. Unidirectional rates of labradorite dissolution near equilibrium were approximately two orders of magnitude slower than far-from-equilibrium rates reported in the literature. Calcite growth occurred near equilibrium and the rates were limited by the labradorite dissolution rates. In the steady state phase, the interplay of these three heterogeneous reactions—labradorite dissolution, calcite growth, and clay precipitation—results in a coupled system that approaches a near-equilibrium state. The system does not reach true equilibrium because labradorite continues to dissolve, albeit at a much slower rate near equilibrium. The overall reaction can be approximated as, Na 0.4 Ca 0.6 Al 1.6 Si 2.4 O 8 + 0.6HCO 3 - + 1·.7H 2 O + 0.4H + → 0.4Na + + 0.6CaCO 3(s) + 0.5Al 2 Si 2 O 5 (OH) 4(s) + 0.6Al(OH) 4 - + 1.4SiO 2 o (aq). The experimental results show that using short-term far-from-equilibrium rate constants would lead to an overestimation of feldspar weathering rates at the Earth’s surface (e.g., basalt weathering and enhanced rock weathering) and CO 2 mineralization in basalt aquifers.

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

Directly resolving surface vs. lattice self-diffusion in iron at the nanoscale using in situ atom probe capabilities

Surface self-diffusion studies on metals under elevated reaction conditions are limited, as it is inherently challenging to unambiguously follow atomic transport across highly-reactive surfaces. Here, quantitative and mechanistic insight into thermally induced atomic transport processes in bcc α-iron at the sub-nanometer level was achieved using isotopic tracer techniques coupled with in situ atom probe tomography (APT) capabilities. Specifically, using a reactor directly connected to the APT, needle-shaped specimens fabricated from epitaxial thin films with an embedded 57 Fe tracer layer were annealed in Ar at 500 °C and 350 °C for 1 hour. Furthermore, the tracer was positioned at various depths in the APT specimen by field evaporation, enabling targeted and simultaneous analysis of lattice and surface diffusion. 57 Fe concentration profiles reveal lattice self-diffusion occurs at 500 °C on the order of ~7 – 9 monolayers, while lattice diffusion is not resolvable at 350 °C. Considerable surface transport was, however, observed at both conditions, where atomic transport over the specimen surface led to the formation of a thin (≤1 nm), isotopically-intermixed layer at the surface. Further, the observed isotopic redistributions at 500 °C were convoluted by additional processes occurring in the subsurface, such as atomic intermixing in correlation with lattice diffusion. However, surface diffusion was determined to be the primary transport process at 350 °C and was thereby quantified. Ultimately, these results demonstrate the significance of surface self-diffusion as a short circuit pathway. More broadly, this approach has the potential to provide detailed insight into (self-)diffusion mechanisms across various materials while targeting site-specific reactions under elevated reaction conditions.

36 MATERIALS SCIENCE↗
DOE OSTI2024

How Rains and Floods Become Groundwater: Understanding Recharge Pathways With Stable and Cosmogenic Isotopes

Anthropogenic climate change leads to increased precipitation intensity and exacerbated droughts in California, challenging the reliability and drought resiliency of water supply. Storing floodwater underground via managed aquifer recharge can mitigate these effects through direct infiltration or streambed infiltration. Seasonally dry streams (arroyos) already play an important part in managing groundwater recharge to the Livermore basin (CA). Understanding how, when and where stormwater and arroyo water infiltrate is critical to effectively utilise this strategy. To track water from recent storms (water year 2022–2023, WY23) into the Livermore Valley Groundwater Basin, we analysed stable water isotopes (δ 18 O and δ 2 H) in combination with naturally occurring radioactive isotopic tracers, sulphur-35 ( 35 S, t ½ = 87 days) and tritium ( 3 H, t ½ = 12.3 years). By comparing measurements of δ 18 O, 35 S and 3 H in arroyos to precipitation and groundwater, we classified the relative age and identified source of recharge to 16 wells near two arroyos. Two wells contained water with recent recharge (from WY23) from local precipitation. One well had recent recharge from variable (precipitation and imported water) sources. One well contained imported water recharge. Three wells contained water from mixed recent and older (pre-WY23) waters, from local precipitation sources. Two wells contained recent recharge from local mine settling ponds. Seven wells had older recharge from local precipitation sources. This combination of isotopes allows us to delineate where local and imported water recharges in this highly managed basin and identify locations where managed aquifer recharge is contributing to rapid groundwater infiltration. Our combined interpretation of isotopic water ages and sources in the context of land use shows that local infiltration of precipitation in open spaces is an important recharge mechanism, in addition to the managed arroyo recharge. Finally, a broader familiarity with 35 S will enable more extensive research on the infiltration of urban floodwaters.

58 GEOSCIENCES↗
DOE OSTI2023

(Project 18-15502) Reducing Uncertainty in Radionuclide Transport Prediction Using Multiple Environmental Tracers (Final Report)

In order to successfully site and design a nuclear waste disposal facility, DOE scientists are required to show safe containment of the radioactive waste for up to 1 million years. A significant hurdle to accurately and convincingly demonstrating disposal safety is predicting the fate of radioactive elements once they enter the groundwater system surrounding the repository. These predictions are often made with computer models, which contain accurate physics of groundwater movement and chemical reactions that occur during groundwater flow. As computer power increases, the physics and chemistry of these computer simulators can become more and more realistic and the physically based error decreases. However, the ability of these computer models to provide accurate predictions in a specific place, over long time periods, requires the scientists and engineers to know the subsurface properties of the Earth that control groundwater movement. In particular, groundwater scientists and engineers need to know the groundwater fluid velocity, which can change over time and strongly vary with location within the groundwater system. Because the Earth’s subsurface cannot be directly seen, and can only be sampled at drilling locations, the properties of the groundwater system are never known completely, and computer models of groundwater transport will always have some amount of uncertainty. This project’s principal goal was to use chemicals and isotope “tracers”, which have been introduced to the groundwater system by natural processes over long time periods, to help inform computer models of the groundwater velocity and subsurface properties. The goal was to calculate how much better predictions of groundwater transport were when these “tracers” were used to inform the computer models.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2021

A mechanistic understanding of oxygen isotopic changes in the Western United States at the Last Glacial Maximum

At the Last Glacial Maximum (LGM), records suggest drier conditions in the northwest United States and wetter conditions in the southwest United States relative to present-day as well as widespread changes in the isotopic composition of water. However, the mechanisms responsible for these changes remain ambiguous. Here, we explore differences in western United States hydroclimate between the LGM and preindustrial with a water isotope tracer enabled Earth System Model. We then use proxy forward models to compare simulated and recorded δ 18 O in speleothems. We find that the pattern of hydroclimate response in the western United States at the LGM relates to a combination of 1) increased frequency and southward shifted wintertime extratropical cyclones in the North Pacific, 2) greater rainout of moisture as it moves over the continent, and 3) reduced evaporation in the cooler LGM climate. The simulated lower δ 18 O of precipitation at the LGM relates predominantly to an increase in cool season moisture removal efficiency, with a secondary contribution from relatively more cool season precipitation. Both surface temperatures and North American ice sheets contribute to these hydroclimate changes at the LGM. Comparisons between δ 18 O from proxy forward models and speleothem records in the western United States show general agreement at the LGM, with increasing depletion moving towards the continental interior. Finally, this study highlights the similarities and differences between hydrologic and δ 18 O changes at the LGM and emphasizes the utility of model-proxy comparison for interpretation.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

The fate of carbon utilized by the subterranean termite Reticulitermes flavipes

Abstract Subterranean termites are ecosystem engineers that modulate the flow of carbon from dead wood to the atmosphere and soil, yet their contributions to the latter pool are largely unaccounted for in carbon cycling models. The fate of C from wood utilized by Reticulitermes flavipes (Kollar) was determined using a reductionist design in a closed system with δ 13 C labeled wood as a stable isotope tracer. The percentage of wood‐based carbon in termite respiratory gases, tissues, and organic deposits (frass and construction materials) was measured for five colonies to budget wood‐C mass distributed into metabolic and behavioral pathways during a 160‐h incubation period. We found that termites emitted 42% of the C from wood as gas (largely as carbon dioxide), returned 40% to the environment as organic deposits (frass and construction materials), and retained 18% in their tissues (whole alimentary tracts and de‐gutted bodies). Our findings affirm that termites are a source of greenhouse gases but are also ecosystem engineers that return approximately half the C from dead wood as organic deposits into their surrounding environment.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Biomolecular budget of persistent, microbial-derived soil organic carbon: The importance of underexplored pools

The details of how soil microorganisms contribute to stable soil organic carbon pools are a pressing knowledge gap with direct implications for soil health and climate mitigation. It is now recognized that microbial necromass contributes substantially to the formation of stable soil carbon. However, the quantification of necromass in soils has largely been limited to model molecules such as aminosugar biomarkers. The abundance and chemical composition of other persistent microbial residues remain unresolved, particularly concerning how these pools may vary with microbial community structure, soil texture, and management practices. We use yearlong soil incubation experiments with an isotopic tracer to quantify the composition of persistent residues derived from microbial communities inhabiting sand or silt dominated soil with annual (corn) or perennial (switchgrass) monocultures. Persistent microbial residues were recovered in diverse soil biomolecular pools including metabolites, proteins, lipids, and mineral-associated organic matter (MAOM). The relative abundances of microbial contributions to necromass pools were consistent across cropping systems and soil textures. The greatest residue accumulation was not recovered in MAOM but in the light density fraction of soil debris that persisted after extraction by chemical fractionation using organic solvents. Necromass abundance was positively correlated with microbial biomass abundance and revealed a possible role of cell wall morphology in enhancing microbial carbon persistence; while gram-negative bacteria accounted for the greatest contribution to microbial-derived carbon by mass at one year, residues from gram-positive Actinobacteria and Firmicutes showed greater durability. Together these results offer a quantitative assessment of the relative importance of diverse molecular classes for generating durable soil carbon.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Thermodynamics, local structure, and transport of protons in triple-conducing oxide, BaCo 0.4 Fe 0.4 Zr 0.1 Y 0.1 O 3-δ (BCFZY4411)

Triple-conducting oxides (TCOs) are an emerging class of mixed ionic and electronically conducting materials that show great promise for oxygen reduction/oxygen evolution (ORR/OER) electrocatalysis—primarily in high-temperature ceramic electrochemical cells— but also in aqueous alkaline environments. Their high activity is attributed, at least in part, to their ability to incorporate and transport three mobile charge carriers: protons, oxygen vacancies, and electron-holes Despite their promise, fundamental studies of TCOs are challenging, as transport dynamics from three charge carriers cannot be fully disentangled via traditional electrical measurement techniques. Characterizing proton dynamics in TCOs is particularly difficult as protons are generally the minority carrier, and their conduction response is typically obscured by the oxygen vacancies and electron holes. Here, we demonstrate successful isolation of the proton behavior in an archetypal TCO, BaCo 0.4 Fe 0.4 Zr 0.1 Y 0.1 O 3-δ (BCFZY4411), using a combination of non-electrical techniques. We determine proton uptake and oxygen non-stoichiometry (δ) using thermogravimetric analysis (TGA). X-ray absorption near edge structure (XANES) and neutron diffraction (ND) are used to validate the oxidation state of Co and the δ values obtained through TGA. We apply 1H solid-state magic-angle-spinning (MAS) nuclear magnetic resonance (NMR) to provide insights into local structure, dynamics, and proton kinetics. Finally, the proton transport properties are further quantified using tracer isotope exchange with time-of-flight secondary ion mass spectrometry (ToF-SIMS). Despite the very low proton concentrations in BCFZY4411 (<0.2% under most conditions), our analysis suggests that the oxygen Manuscript File Click here to view linked References 2 reduction and evolution reactions are nevertheless limited by the oxygen ion kinetics (e.g., oxygen surface exchange) rather than the proton kinetics at the reduced operating temperatures (<500 °C) that are targeted for electrochemical cell applications. These findings provide a comprehensive understanding of proton behavior in BCFZY4411 and pave the way for advancing the fundamental study of TCOs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Arabidopsis ABCG14 forms a homodimeric transporter for multiple cytokinins and mediates long-distance transport of isopentenyladenine-type cytokinins

Phytohormone cytokinins (CKs), primarily including trans-zeatin (tZ) and isopentenyladenine (iP) types, play critical roles in plant growth, development, and stress response. Long-distance transport of trans-zeatin (tZ)-type CKs has been well elucidated. However, long-distance transport of isopentenyladenine (iP)-type CKs remains unknown. Here, we demonstrated that the physiologically characterized ABC transporter AtABCG14 is also involved in long-distance transport of iP-type CKs. Biochemical characterization of AtABCG14 revealed that it forms homodimers and exhibits transporter properties towards multiple CKs, including iP and tZ types. AtABCG14 expression was induced by iP-type CKs in wild type and cyp735a1/a2 (cypDM) double mutant. The triple mutant atabcg14 cypDM exhibited more severe developmental phenotypes than atabcg14 and cypDM. CK quantification and 2 H 6 -iP isotope tracer experiment showed that the root-to-shoot transport of iP-type CKs was suppressed in atabcg14 cypDM. The reciprocal grafting of atabcg14 cypDM and cypDM revealed that AtABCG14 is responsible for the root xylem-loading and shoot phloem-distribution in the shootward transport of iP-type cytokinoins. Additionally, 2 H 6 -iP tracer experiment showed that the rootward transport of iP-type CKs was dependent on AtABCG14 expression in the roots. Collectively, our results demonstrate the long-distance circular transport of iP-type CKs mediated by AtABCG14 and provide new insights into the transport of CKs and other phytohormones.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2026

Interstitialcy-mediated transport in Hematite

Defect transport mechanisms drive the performance of materials in both energy storage and energy generating systems. Iron oxide systems are of particular interest with use cases in both realms. Previous studies of a-Fe2O3 (hematite) determined that the primary point defects at elevated temperature are O vacancies and Fe interstitials, and these defects determine transport rates at temperatures >850°C. However, in advanced nuclear reactor designs, operating temperatures will range between 400-800°C. In this study, we utilize isotopic tracers and the nanoscale resolution of atom probe tomography to determine diffusivities at lower temperatures relevant to nuclear energy generating systems. Supported by a density functional theory informed rate theory model, we find a change from vacancy to interstitialcy-mediated transport < 800°C in the anion lattice.

Yano, Kayla H.↗
DOE OSTI2021

Differences in Mechanism and Rate of Zeolite-Catalyzed Cyclohexanol Dehydration in Apolar and Aqueous Phase

The rate of acid-base catalyzed dehydration of alcohols strongly depends on the solvent and the environment of the acid sites. In this work, we find that Brønsted acidic sites in large-pore zeolites, but not in medium-pore zeolites, catalyze cyclohexanol dehydration in decalin at significantly higher rates than hydrated hydronium ions in aqueous phase. Specifically, the difference in turnover rates between the two solvents amounts to two to three orders of magnitude on H-BEA and H-FAU, while being very modest (within a factor of 2) for H-MFI. Combining kinetic, isotopic tracer and 2H NMR measurements, it is established that cyclohexanol dehydration generally follows an E1-elimination pathway in decalin. A notable exception is the monomer dehydration route on H-MFI, which exhibits a much lower activation energy and a substantially negative activation entropy that appear to be associated with an E2-type mechanism. The C-O bond cleavage displays a dominant degree of rate control in decalin, which stands in contrast to deprotonation (C-H cleavage) being rate-limiting in aqueous-phase dehydration.

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

Kinetic and X-ray Absorption Spectroscopic Analysis of Catalytic Redox Cycles over Highly Uniform Polymetal Oxo Clusters

Metal–organic framework materials (MOFs) offer an opportunity for investigating catalytic properties of polymetal oxo clusters that are highly well defined and uniform in nature, in contrast to other classes of catalysts that may exhibit a propensity toward active site heterogeneity. We report herein a kinetic and X-ray absorption spectroscopy (XAS) analysis of the two-electron oxidation of CO over divalent metal sites in MIL-100(M = Fe, Cr) (MIL = Materials of Institut Lavoisier) materials carrying μ 3 -oxo bridged trimers, and connect observations about the kinetic relevance of redox steps to density functional theory (DFT) predictions published previously. The high degree of uniformity evident from in situ titration measurements leads to a congruence in mechanistic inferences made from steady-state catalytic, transient stoichiometric, isotopic exchange, and isotopic tracer data that all point to a sequential mechanism comprised of separate oxidation and reduction half-cycle steps conjoined by an active oxygen intermediate. In situ XAS data reinforce mechanistic conclusions derived from kinetic analysis, and suggest that the active oxygen intermediate may be more appropriately characterized as an iron-oxyl (Fe 3+ –O – ) rather than an iron-oxo (Fe 4+ =O 2– ) species. The Cr analogue of MIL-100 exhibits contrasting rate features that can be rationalized using an identical sequence of steps as MIL-100(Fe), but with a highly dissimilar set of kinetic parameters that can also be validated using transient stoichiometric experiments. The larger coverages of active oxygen intermediates on MIL-100(Cr) are consistent with predictions from prior DFT studies that suggest more stable and less reactive active oxygen species for metals with lower d-electron counts, and point to metal identity as a lever for precisely controlling the kinetic relevance of oxidation and reduction half-cycles in catalytic redox sequences over polymetal oxo clusters. Importantly, the results presented point to the utility of developing broadly applicable structure–catalytic property relationships over MOF nodes specifically, and highly uniform catalysts more generally.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗