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NASA NTRS1992

Calculations of ion-molecule deuterium fractionation reactions involving HD

Gas-phase chemical models of deuterium fractionation in dense interstellar clouds utilize a small number of exothermic reactions to achieve fractionation. Although HD is a major repository of deuterium, it appears not to exchange deuterium with many molecular ions. Useful semiquantitative reasons have been given for the unusual lack of reactivity of exothermic ion-HD deuterium exchange systems, but quantum chemical studies are needed to understand these ideas in more detail and to determine if the lack of reactivity pertains at very low temperatures not studied in the laboratory, or whether tunneling can drive the reactions. Accordingly, the potential energy surfaces of three representative ion-molecule exchange reactions involving protonated ions and HD have been investigated with ab initio quantum chemical techniques. Our results generally confirm the semiquantitative picture as to which reactions are likely to occur and show that tunneling at low temperatures is unlikely to alter this picture.

Maluendes, Sergio A.↗

NASA NTRS1995

Ignition and combustion of bulk metals under elevated, normal and reduced gravity conditions

This research effort is aimed at providing further insight into this multi-variable dependent phenomena by looking at the effects of gravity on the ignition and combustion behavior of metals. Since spacecraft are subjected to higher-than-1g gravity loads during launch and reentry and to zero-gravity environments while in orbit, the study of ignition and combustion of bulk metals at different gravitational potentials is of great practical concern. From the scientific standpoint, studies conducted under microgravity conditions provide simplified boundary conditions since buoyancy is removed, and make possible the identification of fundamental ignition mechanisms. The effect of microgravity on the combustion of bulk metals has been investigated by Steinberg, et al. on a drop tower simulator. However, no detailed quantitative work has been done on ignition phenomena of bulk metals at lower or higher-than-normal gravitational fields or on the combustion characteristics of metals at elevated gravity. The primary objective of this investigation is the development of an experimental system capable of providing fundamental physical and chemical information on the ignition of bulk metals under different gravity levels. The metals used in the study, iron (Fe), titanium (Ti), zirconium (Zr), magnesium (Mg), zinc (Zn), and copper (Cu) were selected because of their importance as elements of structural metals and their simple chemical composition (pure metals instead of multi-component alloys to avoid complication in morphology and spectroscopic studies). These samples were also chosen to study the two different combustion modes experienced by metals: heterogeneous or surface oxidation, and homogeneous or gas-phase reaction. The experimental approach provides surface temperature profiles, spectroscopic measurements, surface morphology, x-ray spectrometry of metals specimens and their combustion products, and high-speed cinematography of the heating, ignition and combustion stages of the metal specimen. This paper summarizes the results obtained to date from experiments conducted under normal and high-gravity conditions.

Abbud-Madrid, Angel↗

DOE OSTI2021

Understanding the origin of structure sensitivity in hydrodechlorination of trichloroethylene on a palladium catalyst

Periodic density functional theory (DFT) calculations are employed to understand the origin of structure sensitivity in hydrodechlorination (HDC) of trichloroethylene (TCE) over different facets of a palladium catalyst. The HDC reaction is simulated on the terrace (Pd (111) and Pd (100)) and undercoordinated (Pd (211) and Pd (110)) sites of the Pd catalyst. The most stable binding configuration of TCE on the Pd surfaces is observed to be through the di-σ mode of binding, wherein each carbon atom of the TCE molecule is adsorbed atop of the Pd atom. On comparing TCE adsorption over different facets of Pd, a maximum binding energy of –178 kJ mol –1 is calculated over the Pd (110) surface. TCE, upon adsorption on Pd catalyst, undergoes dechlorination followed by hydrogenation of the hydrocarbon intermediates. The activation energies for C–Cl bond dissociation steps are significantly low when compared to the hydrogenation steps. The chlorine released from dechlorination tends to block the active sites, thereby poisoning the surface with high binding energies (B.E > –160 kJ mol –1 ) on all the surfaces. The trend in chlorine binding energies on Pd facets follows: Pd (110) > Pd (211) > Pd (100) > Pd (111). The removal of surface chlorine is facilitated by its reaction with surface hydrogen to form hydrogen chloride. The activation energy for hydrogen chloride formation is calculated to be 90 kJ mol –1 and 88 kJ mol –1 on Pd (111) and Pd (100) terrace sites, respectively and 109 kJ mol –1 and 118 kJ mol –1 on the step Pd (211) and corrugated Pd (110) facets, respectively. This suggests the ease of removal of Cl as HCl from the terrace sites as compared to the step and corrugated sites. The structure sensitivity in the TCE HDC reaction could possibly arise due to the differences in the energetics of Cl removal on different Pd facets. As a result, this mechanistic understanding could provide a rationale for designing suitable catalysts for the HDC of TCE.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

High-Loading Single-Atom Catalyst via On-Surface Synthesis of a Metal-Covalent Organic Framework for Oxygen Reduction Reaction

The development of active catalysts with both high metal efficiency and use of earth abundant metals is the ultimate goal for advancing the required commercially viable and sustainable energy conversion technologies of the future. Metal-organic frameworks (MOFs) have emerged as promising candidates due to their high surface area and tunable active sites. Here, this study aims to fabricate a new type of high metal loading single-atom catalysts (SACs) based on 2D metal-organic covalent organic frameworks (MCOFs) with uniform, active and stable Fe-N 3 sites. The MCOFs were synthesized through an on-surface polymerization process using Fe and melamine as precursors. The polymerization steps were characterized using operando high-pressure scanning tunneling microscopy (HP-STM), in situ X-ray photoelectron spectroscopy (XPS), low-temperature STM (LT-STM), and computational calculations. The synthesized MCOFs demonstrated favorable adsorption and activation of O 2 at the Fe-N 3 sites, and it is predicted to be active for the oxygen reduction reaction (ORR). The surface chemistry and functionality of 2D MCOFs can be rationally designed by varying the metal atoms and organic linkers, offering a versatile platform for diverse applications.

25 ENERGY STORAGE↗

DOE OSTI2024

Mean-Field Ring Polymer Rates Using a Population Dividing Surface

Mean-field Ring Polymer Molecular Dynamics (MF-RPMD) offers a computationally efficient method for the simulation of reaction rates in multi-level systems. Previous work has established that, to model a nonadiabatic state-to-state reaction accurately, the dividing surface must be chosen to explicitly sample kinked ring polymer configurations where at least one bead is in a different electronic state than the others. Building on this, we introduce a population difference coordinate and a kink-constrained dividing surface, and we test the accuracy of the resulting mean-field rate theory on a series of bilinear coupling model systems. Here, we demonstrate that this new MF-RPMD rate approach is efficient to implement and quantitatively accurate for models over a wide range of driving forces, coupling strengths, and temperatures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Analytical Tools to Assess Polymer Biodegradation: A Critical Review and Recommendations

Many petroleum-derived plastic materials are highly recalcitrant and persistent in the environment, posing significant threats to human and ecological receptors due to their accumulation in ecosystems. In recent years, research efforts have focused on advancing biological methods for polymer degradation. Enzymatic depolymerization has emerged as particularly relevant for biobased plastic recycling, potentially scalable for industrial use. Biodegradation involves adsorption to the plastic solid surface, followed by an interfacial reaction, resulting in cleavage of bonds of polymer chains exposed on the surface. Here, widely varying substrate-specific kinetics are observed, with the polymer’s properties possessing a significant impact on the rate of this interfacial catalysis. Thus, there is a critical need for sensitive and accurate characterization of the material surface during and after interfacial depolymerization to fully understand the reaction mechanisms. Here, we provide a critical review of a range of techniques used in the analysis of material surfaces to characterize the chemical, topological, and morphological features relevant to the study of enzymatic biocatalysis, including microscopy techniques, spectroscopic techniques (e.g., X-ray diffraction analysis, Fourier transform infrared attenuated total reflectance spectroscopy, and mass spectrometry detection of analytes associated with degradation). Techniques for evaluation of surface energy and topology in their relevancy for sensitive detection of biological surface modifications are also discussed. In addition, this paper provides an overview of the strengths of these techniques and compares their performance in both sensitivity and throughput, including emerging techniques, which can be useful, particularly for the rapid analysis of the surface properties of polymeric materials in high-throughput screening of candidate biocatalysts. This research serves as a starting point in selecting and applying appropriate methodologies that provide direct evidence to the ongoing biotic degradation of polymeric materials.

Colachis, Matthew↗

DOE OSTI2021

Long-Term Cycling of a Mn-Rich High-Voltage Spinel Cathode by Stabilizing the Surface with a Small Dose of Iron

The high-voltage, cobalt-free spinel cathode LiNi 0.5 Mn 1.5 O 4 (LNMO) is receiving extensive attention for lithium-ion batteries due to its low cost, high operating voltage and energy density, superior power density, and good thermal stability. However, its high operating voltage hampers its stability with commercial electrolytes and makes its practical viability challenging. We present here a Mn-rich LNMO cathode to encourage the disordering of Mn and Ni in the lattice and the incorporation of a small dose of Fe into Mn-rich LNMO (Fe-LNMO) to improve the cycling stability. The introduction of Fe further increases the cation disorder between Mn and Ni, thus enabling a better rate capability. Electron energy loss spectroscopy analysis indicates that Fe is concentrated on the surface, and X-ray photoelectron spectroscopy analysis shows that Fe-LNMO alleviates the aggressive reaction between the cathode surface and the electrolyte, thus stabilizing the interface and cycle life. Furthermore, a full cell assembled with a graphite anode with an areal capacity of 3 mA h cm –2 displays a capacity retention of 90% over 300 cycles. Furthermore, the present work demonstrates an effective way to promote cation disordering and lower the surface reactivity of LNMO with the electrolyte, thereby enhancing the conductivity, stabilizing the cathode–electrolyte interphase, and making LNMO promising for practical applications.

25 ENERGY STORAGE↗

NASA NTRS1996

Catalysis by Dust Grains in the Solar Nebula

In order to determine whether grain-catalyzed reactions played an important role in the chemistry of the solar nebula, we have applied our time-dependent model of methane formation via Fischer-Tropsch catalysis to pressures from 10(exp -5) to 1 bar and temperatures from 450 to 650 K. Under these physical conditions, the reaction 3H2 + CO yields CH4 + H2O is readily catalyzed by an iron or nickel surface, whereas the same reaction is kinetically inhibited in the gas phase. Our model results indicate that under certain nebular conditions, conversion of CO to methane could be extremely efficient in the presence of iron-nickel dust grains over timescales very short compared to the lifetime of the solar nebula.

Kress, Monika E.↗

DOE OSTI2021

Probing adsorbates on La1-xSrxNiO3-d surfaces under humid conditions: implications for the oxygen evolution reaction

Earth-abundant nickel-containing perovskite oxides (ANiO3) are highly active materials for the oxygen evolution reaction (OER). The strong nickel-oxygen (Ni-O) covalency, tunable by A-site chemical substitution, contributes to both bulk and surface material properties like the formation of oxygen vacancies (????••) and OER activity. Here we quantify the coverage of OER relevant adsorbates on a series of La1-xSrxNiO3-d (LSNO, 0 = x = 0.5) epitaxial thin films exposed to humid environments by ambient pressure X-ray photoelectron spectroscopy (AP-XPS). While all LSNO film compositions investigated here have comparable hydroxide coverages at the relative humidities (RHs) probed (1.5 x 10-5 – 0.2 %RH), the amount of under-coordinated surface oxygen increases notably with Sr content. We interpret differences in the free energy of adsorption (?Gads,i) of these OER intermediates, inferred from adsorption isotherms, in the context of proposed ????••-mediated OER mechanisms, consistent with the pH-dependent OER activity observed here for LSNO. We find that Sr incorporation enhances the affinity of LSNO surfaces for these under-coordinated oxygen species, in line with calculations in the literature.

Rare-earth nickelates, ambient pressure-X-ray phot↗

NASA NTRS1978

Chemical reactions in low-g

The Apollo-Soyuz flight experiment, 'Chemical Foams' demonstrated that foams and air/liquid dispersions are much more stable in low-gravity than on the ground. It thus should be possible to conduct unique chemical reactions in space foams. The low-g results and subsequent ground work on the formaldehyde clock reaction indicate that the reaction is strongly influenced by (1) dissociated and undissociated solution species being adsorbed at solid/liquid and gas/liquid surfaces and (2) chemical reaction rates apparently being affected by long-range forces determined by the liquid mass and the extent and nature of all surface interfaces.

Grodzka, P. G.↗

DOE OSTI2022

Facet Impact of CuMn 2 O 4 Spinel Nanocatalysts on Enhancement of the Oxygen Reduction Reaction in Alkaline Media

Surface-structure engineering represents an attractive strategy to optimize the energy conversion performance of nanocatalysts using their deliberately controlled exposed facets. To further exploit the potential of non-PGM-based spinel catalysts for alkaline oxygen reduction reaction (ORR), a cathodic fuel cell reaction, we hereby report a strategy of ORR improvement by controlling the crystallographic facets of ultra-small CuMn 2 O 4 spinel nanocatalysts through a developed colloidal synthesis approach. The synthesis of CuMn 2 O 4 nanocrystals with morphological control relies on the design and selection of the Cu-/Mn-precursors with striking discrepancies in reaction kinetics. Following carbon loading and an annealing post-treatment of the as-synthesized nanocatalysts, the exclusively {101} facet-exposed CuMn 2 O 4 spinel nano-octahedra exhibit improved electrocatalytic activity toward ORR in 1 M KOH, when compared to their spherical counterparts, exhibiting a mass activity (MA) of 37.6 A/g at 0.85 V. After 10,000 cycles of ORR durability test, the nano-octahedra still retain an MA of 24.5 A/g, which is twice that of the CuMn 2 O 4 spinel nanospheres. Structural characterizations after durability testing indicate that the MA decay is likely associated with a decrease in the Mn 3+ fraction and the emergence of Cu + on CuMn 2 O 4 nano-octahedral surfaces. Finally, as a paradigm, this synthesis approach could be extended to other Mn-based spinel nanocatalysts with precise shape control, enabling us to understand and establish the relationship between the surface lattice/valence state and electrocatalytic properties.

36 MATERIALS SCIENCE↗

NASA NTRS1978

The room-temperature dissociation of the compound Au3Si

Three gold-18.6 at.% silicon specimens which were solidified by quenching from above the liquidus temperature have been reexamined after being stored at room temperature for about 8 years. It was found that the 'metastable' compound Au3Si formed on quenching had begun to dissociate by a surface nucleated, solid-state reaction. The reaction front had advanced about 0.2 mm from the surface, leaving a rim of dissociation products. These dissociation products were studied using optical and scanning electron microscopy, electron beam microprobe analysis and an X-ray micro-diffraction technique. It was concluded that the reaction produces elemental gold and silicon, as at higher reaction temperatures, but that the scale of dispersion is so extremely fine that the resulting microstructure cannot be resolved by scanning electron microscopy.

Bhattacharya, D.↗

DOE OSTI2022

Resolving the Heat of Trimethylaluminum and Water Atomic Layer Deposition Half-Reactions

We report that atomic layer deposition (ALD) is a surface synthesis technique that is characterized by self-limiting reactions between gas-phase precursors and a solid substrate. Although ALD processes have been demonstrated that span the periodic table, a greater understanding of the surface chemistry that affords ALD is necessary to enable greater precision, including area- and site-selective growth. We offer new insight into the thermodynamics and kinetics of the trimethylaluminum (TMA) and H 2 O ALD half-reactions with calibrated and time-resolved in situ pyroelectric calorimetry. The half-reactions produce 3.46 and 2.76 eV/Al heat, respectively, which is greater than the heat predicted by computational models based on crystalline Al 2 O 3 substrates and closely aligned with the heat predicted by standard heats of formation. The pyroelectric thin-film calorimeter offers submilisecond temporal resolution that uniquely and clearly resolves precursor delivery and reaction kinetics. Both half-reactions are observed to exhibit multiple kinetic rates, with average TMA half-reaction rates at least 2 orders of magnitude faster than the H 2 O half-reaction kinetics. Comparing the experimental heat with published computational literature and additional first-principles modeling highlights the need to refine our models and mechanistic understanding of even the most ubiquitous ALD reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

The influence of LiH and TiH 2 on hydrogen storage in MgB 2 II. XPS study of surface and near-surface phenomena

We report that Mg(BH 4 ) 2 is a promising solid-state hydrogen storage material, releasing 14.9 wt% hydrogen upon conversion to MgB 2 . The rehydrogenation of MgB 2 is particularly challenging, requiring prolonged exposure to high pressures of hydrogen at high temperature. Here we report an XPS study probing the influence of LiH and TiH 2 on the hydrogen storage properties of MgB 2 in the surface and near-surface regions, as a complementary investigation to a preceding study of the bulk properties. Surface and near-surface properties are important considerations for nanoscale and bulk hydrogen storage materials. If there are reactions occurring at the surface that modify the chemical composition in the near-surface region, species diffusion can alter the chemical composition even deep into the bulk of the material. For LiH/MgB 2 , metastable LiH–B and LiH–Mg species are produced that are more reactive than Bulk MgB 2 . With prolonged glovebox storage, the LiH/MgB 2 material shows increased reactivity towards O and C and enriched levels of Li and B in the near-surface region. In addition, Li induces the growth of Li 2 CO 3 in the surface and near surface regions. Exposing LiH/MgB 2 to hydrogen at 700 bar and 280 °C for 24 h produces borohydride at a temperature 100 °C below the threshold for bulk MgB 2 hydrogenation. In a specifically surface process with macroscopic implications, the hydrogenation conditions also cause Li 2 CO 3 to react with boron hydroxide in the sample to form a Li-deficient glassy lithium borate melt at the interfaces of the particles, bonding them together. Subsequent heating to 380 °C dehydrogenates the borohydride and eliminates the Li-deficient glassy lithium borate. The LiH/MgB 2 material is not reversible because desorption does not lead back to LiH/MgB 2 , but rather to elemental B and Mg metal in the near-surface region. In contrast to LiH, TiH 2 does not react with MgB 2 , despite the favorable thermodynamics for destabilization via TiB 2 formation. Furthermore, high pressure hydrogenation yields only unreacted TiH 2 and MgB 2 in the surface and near-surface regions. Thus, added TiH 2 provides no benefit to MgB 2 hydrogenation, in agreement with the findings of the preceding bulk study.

08 HYDROGEN↗

DOE OSTI2025

Bridging Structural and Chemical Insights: Integrating In Situ Electron Microscopy and X-ray Spectroscopy for Catalysis Research

Environmental transmission electron microscopy probes the local structure, composition, and chemistry of materials under gas environments, while ambient-pressure X-ray photoelectron spectroscopy provides ensemble chemical and electronic structure information in gaseous conditions. Both techniques utilize similar differential pumping schemes to mitigate electron scattering by the gas phase, allowing for unique opportunities to correlate gas–surface interactions across comparable pressure ranges. Their integration has advanced the understanding of various catalytic reactions, including the water–gas-shift reaction, CO oxidation, and surface passivation dynamics. In conclusion, this Mini-Review discusses their methodological advancements, challenges, and potential for further integration with other in situ techniques to address complex catalytic phenomena and guide catalyst design.

36 MATERIALS SCIENCE↗

DOE OSTI2020

The water trimer reaction OH + (H 2 O) 3 → (H 2 O) 2 OH + H 2 O

All important stationary points on the potential energy surface (PES) for the reaction OH + (H 2 O) 3 → (H 2 O) 2 OH + H 2 O have been fully optimized using the “gold standard” CCSD(T) method with the large Dunning correlation-consistent cc-pVQZ basis sets. Three types of pathways were found. For the pathway without hydrogen abstraction, the barrier height of the transition state (TS1) is predicted to lie 5.9 kcal mol -1 below the reactants. The two major complexes (H 2 O) 3 ∙∙∙OH (CP1 and CP2a) are found to lie 6.3 and 11.0 kcal mol -1 , respectively, below the reactants [OH + (H 2 O) 3 ]. For one of the H-abstraction pathways the lowest classical barrier height is predicted to be much higher, 6.1 kcal mol -1 (TS2a) above the reactants. For the other H-abstraction pathway the barrier height is even higher, 15.0 (TS3) kcal mol -1 . Vibrational frequencies and the zero-point vibrational energies connected to the PES are also reported. Fianlly, the energy barriers for the H-abstraction pathways are compared with those for the OH + (H 2 O) 2 and OH + H 2 O reactions, and the effects of the third water on the energetics are usually minor (0.2 kcal mol -1 ).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS2016

Reaction of Basaltic Materials under High-Fidelity Venus Surface Conditions using the Glenn Extreme Environment Rig: First Results

Both historical and current investigations of Venus suggest that atmosphererock interactions play a critical role in the evolution of its atmosphere and crust. We have begun a series of systematic experiments designed to further our understanding of atmosphere-driven weathering and secondary mineralization of basaltic materials that may be occurring on Venus today. Our experiments expose representative igneous phases (mineral, glasses and rocks) to a high-fidelity simulation of Venus surface conditions using the NASA Glenn Extreme Environment Rig (GEER) located at the NASA Glenn Research Center in Cleveland, Ohio. GEER is a very large (800L) vessel capable of producing a long-term, high fidelity simulation of both the physical conditions (750 K and 92 bar) and atmospheric chemistry (down to the ppb-level) asso-ciated with the Venusian surface. As of this writing we have just finished the first of several planned experiments: a 42-day exposure of selected mineral, rocks and volcanic glasses. Our goal is to identify and prioritize the reactions taking place and better our understanding of their importance in Venus' climate history.

Venus surface↗

DOE OSTI2021

Reaction paths of methane activation and oxidation of surface intermediates over NiO on Ceria-Zirconia catalysts studied by In-situ FTIR spectroscopy

Methane activation over NiO/Ce 0.82 Zr 0.18 O 2 catalysts synthesized by combustion synthesis is studied by in-situ IR spectroscopy and correlated to the properties and oxygen speciation of the catalyst. Through XRD, H 2 -TPR, and pyridine adsorption followed by FTIR spectroscopy, the reducibility and Lewis acidity of the catalysts are assessed. In-situ FTIR spectroscopy is used to monitor the methane activation on catalyst surfaces. Complex IR features of methane-derived surface species are observed and are attributed to the formation of surface alkyl/alkoxy, aldehyde, formate/carbonate, and aromatic species. A data analysis algorithm is developed to evaluate the evolution of different surface species over time. The formation of formate and carbonate species is driven by adsorbed surface oxygen, while less reactive oxygen species associated with NiO allow for the production of aromatics and alkoxy intermediates. Finally, by tuning the reducibility and Lewis acidity of the catalyst, the selectivity to alkoxy intermediates can be improved.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗