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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 1,711 records · Page 95
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Characterization of the Bacterioferritin/Bacterioferritin Associated Ferredoxin Protein–Protein Interaction in Solution and Determination of Binding Energy Hot Spots

Mobilization of iron stored in the interior cavity of BfrB requires electron transfer from the [2Fe–2S] cluster in Bfd to the core iron in BfrB. A crystal structure of the Pseudomonas aeruginosa BfrB:Bfd complex revealed that BfrB can bind up to 12 Bfd molecules at 12 structurally identical binding sites, placing the [2Fe–2S] cluster of each Bfd immediately above a heme group in BfrB. We report here a study aimed at characterizing the strength of the P. aeruginosa BfrB:Bfd association using surface plasmon resonance and isothermal titration calorimetry as well as determining the binding energy hot spots at the protein–protein interaction interface. The results show that the 12 Bfd-binding sites on BfrB are equivalent and independent and that the protein–protein association at each of these sites is driven entropically and is characterized by a dissociation constant ( K d ) of approximately 3 μM. Determination of the binding energy hot spots was carried out by replacing certain residues that comprise the protein–protein interface with alanine and by evaluating the effect of the mutation on K d and on the efficiency of core iron mobilization from BfrB. The results identified hot spot residues in both proteins [L B 68 , E A 81 , and E A 85 in BfrB (superscript for residue number and subscript for chain) and Y 2 and L 5 in Bfd] that network at the interface to produce a highly complementary hot region for the interaction. The hot spot residues are conserved in the amino acid sequences of Bfr and Bfd proteins from a number of Gram-negative pathogens, indicating that the BfrB:Bfd interaction is of widespread significance in bacterial iron metabolism.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2016

Structural and Functional Characterization of Aerobactin Synthetase IucA from a Hypervirulent Pathotype of Klebsiella pneumoniae

Iron is a vital mineral nutrient required by virtually all life forms to prosper; pathogenic bacteria are no exception. Despite the abundance of iron within the human host, highly regulated iron physiology can result in exceedingly low levels of iron bioavailable to prospective invading bacteria. To combat this scarcity of iron, many pathogenic bacteria have acquired specific and efficient iron acquisition systems, which allow them to thrive in iron-deficient host environments. One of the more prominent bacterial iron acquisition systems involves the synthesis, secretion, and reuptake of small-molecule iron chelators known as siderophores. Aerobactin, a citrate-hydroxamate siderophore originally isolated nearly 50 years ago, is produced by a number of pathogenic Gram-negative bacteria. Aerobactin has recently been demonstrated to play a pivotal role in mediating the enhanced virulence of a particularly invasive pathotype of Klebsiella pneumoniae (hvKP). Toward further understanding of this key virulence factor, we report the structural and functional characterization of aerobactin synthetase IucA from a strain of hvKP. The X-ray crystal structures of unliganded and ATP-bound forms of IucA were solved, forming the foundation of our structural analysis. Small angle X-ray scattering (SAXS) data suggest that, unlike its closest structurally characterized homologues, IucA adopts a tetrameric assembly in solution. Finally, we employed activity assays to investigate the substrate specificity and determine the apparent steady-state kinetic parameters of IucA.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2018

Sensitivity-Enhanced 207 Pb Solid-State NMR Spectroscopy for the Rapid, Non-Destructive Characterization of Organolead Halide Perovskites

Here, organolead halide and mixed halide perovskites (CH 3 NH 3 PbX 3 , CH 3 NH 3 PbX 3– n Y n , X and Y = Cl – , Br – , or I – ) are promising materials for photovoltaics and optoelectronic devices. 207 Pb solid-state NMR spectroscopy has previously been applied to characterize phase segregation and halide ion speciation in mixed halide perovskites. However, NMR spectroscopy is an insensitive technique that often requires large sample volumes and long signal averaging periods. This is especially true for mixed halide perovskites, which give rise to extremely broad 207 Pb solid-state NMR spectra. Here, we quantitatively compare the sensitivity of the various solid-state NMR techniques on pure and mixed halide organolead perovskites and demonstrate that both fast MAS and DNP can provide substantial gains in NMR sensitivity for these materials. With fast MAS and proton detection, high signal-to-noise ratio two-dimensional (2D) 207 Pb– 1 H heteronuclear correlation (HETCOR) NMR spectra can be acquired in less than half an hour from only ca. 4 μL of perovskite material. Modest relayed DNP enhancements on the order of 1 to 20 were obtained for perovskites. The cryogenic temperatures (110 K) used for DNP experiments also provide a significant boost in sensitivity. Consequently, it was possible to obtain the 207 Pb solid-state NMR spectrum of a 300 nm thick model thin film of CH 3 NH 3 PbI 3 in 34 h by performing solid-state NMR experiments with a sample temperature of 110 K. This result demonstrates the possibility of using NMR spectroscopy for characterization of perovskite thin films.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Small-angle Neutron Scattering (SANS) Characterization of Clay- and Carbonate-rich Shale at Elevated Pressures

Unconventional oil and gas from shale formations have emerged as some of the fastest growing energy resources in the United States, providing both cleaner energy to consumers and reducing the nation’s reliance on energy imports. To properly harness these important natural resources, the nanopore structure of associated shales must be fully understood, particularly under hydraulic fracturing conditions, where they are exposed to both overburden compressive and hydrostatic fluid pressures. The current study uses small-angle neutron scattering (SANS) to characterize pore structure, including porosity, pore accessibility, and pore size distribution, in the 1–100 nm regime at elevated pressures for mineralogically distinct clay- and carbonate-rich shales from the Permian Basin. Unlike typical porosity measurement techniques, SANS is uniquely capable of characterizing both open and closed porosity, allowing measurement of how pore accessibility changes with pressure and determination of the size range of accessible versus inaccessible pores. The porosity of the clay-rich shale was 7.7%, compared to 0.51% for the carbonate-rich shale. However, only 2.6% of the nanopores in the carbonate-rich shale were inaccessible to water at 8 kPSI (55.1 MPa) compared to 7.8% for the clay-rich shale. Furthermore, our analyses indicated that the closed pores fall within distinct size ranges, likely corresponding with the chemical nature of the pore host material. These results provide valuable insight into the effects of shale petrophysical properties on hydrocarbon extraction from unconventional reservoirs.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Characterization of Resistances of a Capacitive Deionization System

Capacitive deionization (CDI) is a promising desalination technology, which operates at low pressure, low temperature, requires little infrastructure, and has the potential to consume less energy for brackish water desalination. However, CDI devices consume significantly more energy than the theoretical thermodynamic minimum, and this is at least partly due to resistive power dissipation. We here report our efforts to characterize electric resistances in a CDI system, with a focus on the resistance associated with the contact between current collectors and porous electrodes. We present an equivalent circuit model to describe resistive components in a CDI cell. We propose measurable figures of merit to characterize cell resistance. We also show that contact pressure between porous electrodes and current collectors can significantly reduce contact resistance. As a result, we propose and test an alternative electrical contact configuration which uses a pore-filling conductive adhesive (silver epoxy) and achieves significant reductions in contact resistance.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Ion-Exchange Membrane-Centric Durability Testing and Degradation Characterization for Industry-Relevant CO 2 Reduction

Electrochemical CO 2 reduction is a promising conversion process for producing value-added fuels and chemicals from electricity and CO 2 as a sustainable carbon feedstock to domestically produce fuels and chemicals from industrial waste. Having reached industrially viable performance metrics with small-scale CO 2 electrolysis cells, the field must now increasingly focus on extending the device durability of large stacks to achieve equivalent metrics for 35,000+ hours to decrease maintenance and capital costs. Reported device lifetimes have increased in recent years, with the longest stability studies for CO, ethylene, and formic acid production being published in 2024–2025 with operation times of 4500, 1000, and 5200 h, respectively. Unfortunately, significant extension of the device durability is still required. Here, we provide an overview of ion-exchange membranes (IEMs) and provide insight into the variety of degradation mechanisms that must be overcome to enable the community to meet durability targets. In an effort to accelerate the extension of device lifetimes, we propose a general approach for characterizing CO 2 electrolysis cell degradation before and after durability testing to better elucidate the mechanisms and failure modes of IEMs in zero-gap cells. Furthermore, we encourage the adoption of operando characterizations in tandem with accelerated stress and durability tests, postulating that their combined applications will be increasingly valuable. We hope that this perspective motivates future durability studies to evaluate degradation across the entire electrolysis cell.

09 BIOMASS FUELS↗
DOE OSTI2020

Synthesis, Characterization, and Biological Activity of Hybrid Thiosemicarbazone–Alkylthiocarbamate Metal Complexes

A series of hybrid ligands (H 2 L 1 –H 2 L 3 ) derived from 4-methyl-3-thiosemicarbazide and hydrazinecarbothioic acid O-alkyl esters were synthesized and characterized by NMR. The ligands were chelated with copper (4–6), nickel (7–9), and zinc (10–12) and characterized by spectroscopy, electrochemistry, and single crystal X-ray crystallography. The chelated metals displayed substantial anodic shifts in the Cu II/I reduction potential of ~160 mV relative to their bis(thiosemicarbazone) analogues. The metal chelates 4–12 were evaluated for potential anticancer activity by MTT assays, and selected results were confirmed by clonogenic and trypan blue assays. The copper derivatives 4 and 6 were found to have potent and cancer-selective antiproliferative effects, with GI 50 values less than 100 nM in A549 lung adenocarcinoma cells compared with at least 20-fold less activity in IMR90 nonmalignant lung fibroblasts. In comparison, the nickel complexes were much less active and had little cancer-selectivity. Varying by ligand, the zinc complexes were less potent or had comparable activity compared to that of the corresponding copper complex. UV–visible spectroscopy indicated that zinc complex 10 was transmetalated in the presence of equimolar copper, whereas nickel complex 7 was not. Copper complexes 4 and 6 were also assessed in the NCI60 screen and were found to have cytotoxic activity against most solid tumor cell lines. In MTT assays, 4 and 6 were substantially more active against A549 cancer cells than Cu(ATSM) and were more cancer-selective (for A549 compared to IMR-90) than Cu(GTSM). Finally, our results suggest that hybrid thiosemicarbazone–alkylthiocarbamate copper complexes have potential for development as new anticancer agents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Synthesis and Characterization of a Tetrapodal NO 4 4– Ligand and Its Transition Metal Complexes

In this paper, we present the synthesis and characterization of alkali metal salts of the new tetraanionic, tetrapodal ligand 2,2'-(pyridine-2,6-diyl)bis(2-methylmalonate) (A4[PY(CO 2 ) 4 ], A = Li + , Na + , K + , and Cs + ), via deprotection of the neutral tetrapodal ligand tetraethyl 2,2'-(pyridine-2,6-diyl)bis(2-methylmalonate) (PY(CO2Et) 4 ). The [PY(CO 2 ) 4 ] 4- ligand is composed of an axial pyridine and four equatorial carboxylate groups and must be kept at or below 0 °C to prevent decomposition. Exposing it to a number of divalent first-row transition metals cleanly forms complexes to give the series K 2 [(PY(CO 2 ) 4 )M(H 2 O)] (M = Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ , Zn 2+ ). The metal complexes were comprehensively characterized via single-crystal X-ray diffraction,1H NMR and UV-vis absorption spectroscopy, and cyclic voltammetry. Crystal structures reveal that [PY(CO 2 ) 4 ] 4- coordinates in a pentadentate fashion to allow for a nearly ideal octahedral coordination geometry upon binding an exogenous water ligand. Additionally, depending on the nature of the charge-balancing countercation (Li + , Na + , or K + ), the [(PY(CO 2 ) 4 )M(H 2 O)] 2- complexes can assemble in the solid state to form one-dimensional channels filled with water molecules. Aqueous electrochemistry performed on [(PY(CO 2 ) 4 )M(H 2 O)] 2- suggested accessible trivalent oxidation states for the Fe, Co, and Ni complexes, and the trivalent Co 3+ species [(PY(CO 2 ) 4 )Co(OH)] 2- could be isolated via chemical oxidation. Finally, the successful synthesis of the [PY(CO 2 ) 4 ] 4- ligand and its transition metal complexes illustrates the still-untapped versatility within the tetrapodal ligand family, which may yet hold promise for the isolation of more reactive and higher-valent metal complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Mn(III)-Iodosylarene Porphyrins as an Active Oxidant in Oxidation Reactions: Synthesis, Characterization, and Reactivity Studies

Mn(III)-iodosylarene porphyrin adducts, [Mn(III)(ArIO)(Porp)] + , were synthesized by reacting electron-deficient Mn(III) porphyrin complexes with iodosylarene (ArIO) at –60 °C and characterized using various spectroscopic methods. The [Mn(III)(ArIO)(Porp)] + species were then investigated in the epoxidation of olefins under stoichiometric conditions. In the epoxidation of olefins by the Mn(III)-iodosylarene porphyrin species, epoxide was formed as the sole product with high chemoselectivities and stereoselectivities. For example, cyclohexene oxide was formed exclusively with trace amounts of allylic oxidation products; cis - and trans -stilbenes were oxidized to the corresponding cis- and trans-stilbene oxides, respectively. In the catalytic epoxidation of cyclohexene by an electron-deficient Mn(III) porphyrin complex and s PhIO at low temperature (e.g., –60 °C), the Mn(III)-iodosylarene porphyrin species was evidenced as the active oxidant that effects the olefin epoxidation to give epoxide as the product. However, at high temperature (e.g., 0 °C) or in the case of using an electron-rich manganese(III) porphyrin catalyst, allylic oxidation products, along with cyclohexene oxide, were yielded, indicating that the active oxidant(s) was not the Mn(III)-iodosylarene adduct but probably high-valent Mn-oxo species in the catalytic reactions. We also report the conversion of the Mn(III)-iodosylarene porphyrins to high-valent Mn-oxo porphyrins under various conditions, such as at high temperature, with electron-rich porphyrin ligand, and in the presence of base (OH–). The present study reports the first example of spectroscopically well-characterized Mn(III)-iodosylarene porphyrin species being an active oxidant in the stoichiometric and catalytic oxidation reactions. In conclusion other aspects, such as one oxidant versus multiple oxidants debate, also were discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Electronic, Magnetic, and Theoretical Characterization of (NH 4 ) 4 UF 8 , a Simple Molecular Uranium(IV) Fluoride

The simple system of tetraammonium octafluorouranate is employed to derive a fundamental understanding of the uranium–fluorine interaction. The structure is composed of isolated molecules, enabling a detailed examination of the U 4+ (ƒ 2 ) ion. Characterization of single-crystals by X-ray diffraction, absorption spectroscopy, and magnetic analysis up to 45 T is combined with extensive theoretical treatment by CASSCF. The influence of different active spaces and representations of the structure is examined in the context of the experimental evidence. The Interacting Quantum Atoms method (IQA) is used to examine the nature of the U–F bond, concluding that there is a non-negligible degree of covalent character (9% of the total bond energy) in [UF8] 4- . For the structural and theoretical reasons discussed herein, it is proposed that the structure of (NH 4 ) 4 UF 8 may be appropriately employed as a benchmark compound for future theoretical characterization of U(IV).

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2024

Pairing a Global Optimization Algorithm with EXAFS to Characterize Lanthanide Structure in Solution

Ensemble-average sampling of structures from ab initio molecular dynamics (AIMD) simulations can be used to predict theoretical extended X-ray absorption fine structure (EXAFS) signals that closely match experimental spectra. However, AIMD simulations are time-consuming and resource-intensive, particularly for solvated lanthanide ions, which often form multiple nonrigid geometries with high coordination numbers. Here, to accelerate the characterization of lanthanide structures in solution, we employed the Northwest Potential Energy Surface Search Engine (NWPEsSe), an adaptive-learning global optimization algorithm, to efficiently screen first-shell structures. As case studies, we examine two systems: Eu(NO 3 ) 3 dissolved in acetonitrile with a terpyridine ligand (terpyNO 2 ), and Nd(NO 3 ) 3 dissolved in acetonitrile. The theoretical spectra for structures identified by NWPEsSe were compared to both experimental and AIMD-derived EXAFS spectra. The NWPEsSe algorithm successfully identified the proper solvation structure for both Eu(NO 3 ) 3 (terpyNO 2 ) and Nd(NO 3 )(acetonitrile) 3 , with the calculated EXAFS signals closely matching the experimental spectra for the Eu-ligand complex and showing good similarity for the Nd salt; the better agreement with the ligand-containing structure is attributed to a less dynamic coordination environment due to the rigid ligand. The key advantage of the global optimization algorithm lies in its ability to sample the coordination environment across the potential energy surface and reduce the time required to identify structures from generally a month to within a week. Additionally, this approach is versatile and can be adapted to characterize main-group metal complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Toward Automated Tools for Characterization of Molecular Porosity

The emerging advanced porous materials, e.g. extended framework materials and porous molecular materials, offer an unprecedented level of control of their structure and function. The enormous possibilities for tuning these materials by changing their building blocks mean that, in principle, optimally performing materials for a variety of applications can be systematically designed. However, the process of finding a set of optimal structures for a given application requires computational high-throughput tools to analyze and sieve through many candidate materials. In particular, in the case of porous molecular materials, the analysis and selection of a molecule is one of the key aspects as the structure of the molecule determines the structure of the resulting material, and very often the porosity of the molecule significantly contributes to the porous properties of the resulting material. In this work, we introduce definitions and algorithms to characterize porosity at the molecular level, along with a software implementation of these algorithms. We demonstrate applications of the software tool in the discovery and characterization of porous molecules among ca. 94 million molecules currently enlisted in the PubChem database.

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

Cu(II) Stability and UV-Induced Electron Transfer in a Metal–Organic Hybrid: An EPR, DFT, and Crystallographic Characterization of Copper-Doped Zinc Creatininium Sulfate

Single-crystal X-ray diffraction and electron paramagnetic resonance (EPR) spectroscopic experiments, complemented by quantum chemical DFT calculations, were carried out on the copper-doped metal–organic hybrid and Tutton salt analogue zinc creatininium sulfate to determine its crystal structure, to characterize the electronic structure of the doped Cu(II) binding site, and to propose a pathway for an excited-state, proton-coupled electron transfer (PCET) process in UV-exposed crystals. The crystal structure is isomorphous to that of cadmium creatininium sulfate, which has the transition ion, not in direct coordination with the creatinine, but forming a hexahydrate complex, which is bridged to a creatininium through an intervening sulfate ion. The EPR g (2.446, 2.112, 2.082) and copper hyperfine (A Cu : -327, -59.6, 10.8 MHz) tensor parameters are consistent with doped copper replacing host zinc in the metal–hexahydrate complex. These parameters are similar to those observed for copper hexahydrate in doped Tutton salt systems at low temperature, where the unpaired electron occupies mainly the copper 3d x 2 –y 2 orbital. At room temperature in the Tutton systems, vibration couplings stemming from a dynamic Jahn–Teller effect cause tensor averaging which results in a reduction in their maximum g-tensor and hyperfine tensor values. However, like for the doped isomorphous Cd creatinine crystal, the Cu(II) EPR exhibits little, or no room temperature averaging compared to its low temperature pattern. Samples exposed to 254 nm UV light generate a carbon-centered free radical species, characterized by an isotropic g-tensor (g = 2.0029) and an alpha-proton hyperfine coupling (-24 -14 +4 G). These parameters identify it as a creatinine radical cation formed by the oxidative release of one of its C2 methylene hydrogens. DFT calculations confirm the unpaired electronic structures of both the Cu(II) site and free radical. The growth in radical concentration with an increase in the UV exposure time coincides with a decrease in the copper EPR signal, indicating a coupled light-induced oxidation reduction process. A comparison of the crystal structure with the EPR parameters and DFT results provides evidence for a UV-induced PCET.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Cation, Anion, and Radical Isomers of C4H4N: Computational Characterization and Implications for Astrophysical and Planetary Environments

Nitrogen-containing ions and molecules in the gas phase have been detected in non-Earth environments such as dark molecular clouds and more recently in the atmosphere of Saturn's moon Titan. These molecules may serve as precursors to larger heterocyclic structures that provide the foundation of complex biological molecules. On Titan, molecules of m/z 66 have been detected by the Cassini mission, and species of the empirical formula C 4 H 4 N may contribute to this signature. We have characterized seven isomers of C 4 H 4 N in anionic, neutral radical, and cationic states using density functional theory. Structures were optimized using the range-separated hybrid ωB97X-V with the cc-pVTZ and aug-cc-pVTZ basis sets. Anionic and radical C4H4N favor cyclic structures with aromatic and quasi-aromatic electron arrangements, respectively. Interestingly, ionization from the radical surface to the cation induces significant changes in structural stability, and the global minimum for positively charged isomers is CH 2 CCHCNH + , a pseudo-linear species reminiscent of cyanoallene. Select formation pathways to these structures from Titan's existing or postulated gas-phase species, reactions that are also relevant for other astrophysical environments, are discussed. By characterizing C 4 H 4 N isomers, we have identified energetically stable anionic, radical, and cationic structures that may be present in Titan's atmosphere and dark molecular clouds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Characterization of Aβ Monomers through the Convergence of Ensemble Properties among Simulations with Multiple Force Fields

We found that amyloid β (Aβ) monomers represent a base state in the pathways of aggregation that result in the fibrils and oligomers implicated in the pathogenesis of Alzheimer’s disease (AD). The structural properties of these intrinsically disordered peptides remain unclear despite extensive experimental and computational investigations. Further, there are mutations within Aβ that change the way the peptide aggregates and are known to cause familial AD (FAD). Here, we analyze the ensembles of different isoforms (Aβ42 and Aβ40) and mutants (E22Δ, D23N, E22K, E22G, and A2T in Aβ40) of Aβ generated with all-atom replica exchange molecular dynamics (REMD) simulations on the μs/replica time scale. These were run using three different force field/water model combinations: OPLS-AA/L and TIP3P (“OPLS”), AMBER99sb-ILDN and TIP4P-Ew (“ILDN”), as well as CHARMM22* and TIP3SP (“CHARMM”). Despite fundamental changes in simulation parameters, we find that the resulting ensembles demonstrate a strong convergence in structural properties. In particular, antiparallel contacts between L17–A21 and A30–L34 are prevalent in ensembles of Aβ40, directly forming β sheets in the OPLS and ILDN combinations. A21–A30 commonly forms an interceding region that rarely interacts with the rest of the peptide. Further, Aβ42 contributes new β hairpin motifs involving V40–I41 in both OPLS and ILDN. However, the structural flexibility of the central region and the electrostatic interactions that characterize it are notably different between the different conditions. Further, for OPLS, each of the FAD mutations disrupts central bend character and increases the polymorphism of antiparallel contacts across the central region. However, the studied mutations in the ILDN set primarily encourage more global contacts involving the N-terminus and the central region, and promote the formation of new β topologies that may seed different aggregates involved in disease phenotypes. Furthermore, these differences aside, the large degree of agreement between simulation sets across multiple force fields provides a generalizable characterization of Aβ that is also consistent with experimental data and models.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Characterizing Complex Gas–Solid Interfaces with in Situ Spectroscopy: Oxygen Adsorption Behavior on Fe–N–C Catalysts

Electrocatalysts for the oxygen reduction reaction within polymer electrolyte membrane fuel cells based on iron, nitrogen, and carbon elements (Fe–N–C) are receiving significant research attention as they offer an inexpensive alternative to catalysts based on platinum-group metals. Although both the performance and the fundamental understanding of Fe–N–C catalysts have improved over the past decade, there remains a need to differentiate the relative activity of different active sites. Toward this goal, our study is focused on characterizing the interactions between O 2 and a set of five structurally different Fe–N–C materials. Detailed characterization of the Fe speciation was performed with 57 Fe Mössbauer spectroscopy and soft X-ray absorption spectroscopy of the Fe L 3,2 -edge, whereas nitrogen chemical states were investigated with X-ray photoelectron spectroscopy (XPS). In addition to initial sXAS and XPS measurements performed in ultra-high vacuum (UHV), measurements were also performed (at the identical location) in an atmosphere of 100 mTorr of O 2 at 80 °C (O 2 -rich). XPS and sXAS results reveal the presence of several types of FeNxCy adsorption sites. FeNxCy sites that are proposed as the most active ones do not show significant change (based on the techniques used in this study) when their environment is changed from UHV to O 2 -rich. Correlation with Mössbauer and sXAS results suggests that this is most likely due to the persistence of strongly adsorbed O 2 molecules from their previous exposure to air. However, other species do show spectroscopic changes from UHV conditions to O 2 -rich. This implies that these sites have a weaker interaction with O 2 that results in their desorption in vacuum conditions and re-adsorption when exposed to the O 2 -rich environment. The nature of these weakly and strongly O 2 -adsorbing FeN x C y sites is discussed in the context of different synthetic and processing parameters employed to fabricate each of these five Fe–N–C materials.

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

Preparation and Characterization of Model Homotopic Catalysts: Rh Adatoms, Nanoparticles, and Mixed Oxide Surfaces on Fe 3 O 4 (001)

The atomic-level characterization of active sites is essential to understanding the mechanisms behind catalytic reactions. In this study, using scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS), we follow the morphological changes of a model Rh catalysts supported on Fe 3 O 4 (001) as a function of temperature and Rh coverage. Here, we identify the preparation conditions leading to model catalysts containing homotopic or nearly homotopic Rh species bound as adatoms, small clusters, substitutional within the Fe 3 O 4 (001), and nanoparticles. Adsorbates such as CO and CO 2 are further subsequently used to characterize the properties of different Rh sites. Using temperature programmed desorption (TPD), we demonstrate that adatoms, clusters, and nanoparticles exhibit high-temperature CO desorption (250-600 K). Strong binding on such sites further allows for CO oxidation to CO 2 via the Mars-van-Krevelen mechanism. In contrast, CO 2 was found to interact weakly with all Rh sites. Differences in desorption temperature enable the use of CO and CO 2 as titration methods for nanoparticles and Fe 3 O 4 (001), respectively. A small quantity of CO 2 was found to be reduced to CO on Rh adatoms and clusters.

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

In Situ Attenuated Total Reflectance Infrared Spectroelectrochemistry (ATR-IR-SEC) for the Characterization of Molecular Redox Processes on Surface-Proximal Doped Silicon ATR Crystal Working Electrodes

In situ mid-infrared spectroscopy is a powerful technique for understanding the mechanism of CO 2 reduction (CO 2 R) catalysts because it enables the direct detection of catalytic intermediates and products. Moreover, spectroelectrochemistry (SEC), the coupling of spectroscopy with electrochemistry, allows spectroscopic changes to be correlated with applied potentials to reveal potential-dependent intermediates that are often relevant to photoelectrochemical reactions. Hybrid photoelectrodes, comprised of a narrow bandgap semiconductor, like silicon (Si), with a covalently-linked molecular catalyst, are a promising platform for sunlight-driven catalysis, but characterization of the catalytic mechanism(s) is challenging under photoelectrochemical conditions, particularly when the catalyst is present in monolayer or less concentrations. Here, we have developed a new strategy to use multiple-reflection attenuated total reflectance IR spectroscopy (ATR-IR) coupled with electrochemistry to characterize catalysts directly integrated with a semiconductor surface under applied potential. We show that by surface-proximal n-type or p-type doping of the top ~100-200 nm of the crystal surface, Si ATR crystals can be used simultaneously as the internal reflection element and semiconductor working electrode for ATR-IR-SEC measurements. The surface-proximal doping strategy yields a quasi-equipotential surface with excellent infrared transparency that would have been compromised by free carrier absorption if the crystal was uniformly doped. This approach permits the catalytically-active functionalized surface to be directly probed without modification and overcomes signal-to-noise limitations of other strategies that use separately deposited working electrodes on Si ATR crystals. Proof-of-concept ATR-IR-SEC spectra were collected during the reduction and oxidation of monolayers of Re- and Ru-based transition metal carbonyl complexes, respectively, verifying the viability of the technique to probe redox processes associated with CO 2 R catalysts on Si electrode surfaces with high sensitivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗