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All sources NASA NTRS DOE OSTI

DOE OSTI2022

Carboxylic acid ligand substituent impacts hydrosilylation activity of platinum single atom catalysts on ceria

Current industrially employed hydrosilylation catalysts rely on homogeneous platinum catalysts which are not recovered after the reaction. To eliminate this issue, our group has been working to optimize recyclability of heterogeneous platinum single atom catalysts (SACs) on ceria via 1,10-phenanthroline-5,6-dione ligands (PDO), which incorporates mono (PDO-C) and dicarboxylic acid (PDO-C2) groups in the 2- and 9-position of PDO ligand to increase metal–surface interaction. DRIFTS results confirm carboxylic acid coordination to the terminal hydroxy groups of the ceria surface. New catalyst synthesis conditions wherein PDO was combined with the metal prior to exposure to the surface allow control of Pt oxidation state on the surface. Here, the highest metal loading was observed for PDO and PDO-C, correlating with improved catalytic recyclability compared to the PDO-C2 ligand. It is proposed that the location of the carboxylic acid groups and the steric effects can explain the lower activity and metal loading for PDO-C2 ligands. Post-reaction XPS and DRIFTS spectra show the appearance of new Si and O species on the catalyst during the hydrosilylation reaction, indicating the silane reagent is depositing on the surface. The silane coverage and leaching of catalyst from the surface is the cause for the reduced catalytic activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS2001

Combustion of Metals in Reduced-Gravity and Extraterrestrial Environments

As a result of the ongoing exploration of Mars and the several unmanned and possibly manned missions planned for the near future, increased attention has been given to the use of the natural resources of the planet for rocket propellant production and energy generation. Since the atmosphere of Mars consists of approximately 95% carbon dioxide (CO2), this gas is the resource of choice to be employed for these purposes. Since many metals burn vigorously with CO2, these may be used as an energy source or as propellants for a research vehicle on the surface of Mars. Shafirovich and Goldshleger conducted experiments with spherical particles up to 2.5 mm in diameter and found that the burning process was controlled by diffusion and that the particles exhibited pulsating combustion due to superheating of the Mg vapor trapped inside a protective oxide shell. They also proposed a reaction mechanism based on the gas-phase reaction, Mg + CO2 yields MgO + CO and the heterogeneous reaction Mg + CO yields MgO + C occurring on the sample surface. In all the above studies with large Mg particles, the burning process is invariably influenced by strong convective currents that accelerate the combustion reaction and shorten the burning times. Although these currents are nearly absent in the burning of small particles, the high emissivity of the flames, rapid reaction, and small length scales make the gathering of any useful information on burning rates and flame structure very difficult. The goal of this investigation is to provide a detailed study of flame structure by taking advantage of large, free-floating spherical metal samples and their corresponding long burning times available in a weightless environment. The use of reduced gravity is essential to eliminate the intrusive buoyant flows that plague high temperature metal reactions, to remove the destructive effect of gravity on the shape of molten metal samples, and to study the combustion behavior of metals in the presence of solid oxides undisturbed by natural convection. This work presents the most complete modeling of metal particle burning to date for Mg with CO2 and O2.

Branch, M. C.↗

DOE OSTI2020

New findings and current controversies in the reaction of ruthenium red and ammonium cerium(iv) nitrate: focus on the precipitated compound

Finding the true catalyst has always been a challenging step toward the exploration, understanding, and design of catalytic systems for water-oxidation reaction. Many homogeneous and heterogeneous transition metal complexes have been reported that can undergo a complete transformation to the true catalysts during water-oxidation reaction. Furthermore, the transformation of the previously-explored ruthenium red ([(NH 3 ) 5 RuORu(NH 3 ) 4 ORu(NH 3 ) 5 ]Cl 6 ) catalyst in the presence of ammonium cerium(IV) nitrate is reported. For the first time, it is reported that a heterogeneous nano-sized ruthenium–cerium compound is formed by the electrostatic interaction of [(NH 3 ) 5 RuORu(NH 3 ) 4 ORu(NH 3 ) 5 ], 6+/7+ nitrate ions, and the products of the reduction of ammonium cerium(IV) nitrate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Deciphering the Evolution of Current Distribution in Hybrid Silver Vanadium Oxide / Carbon Monofluoride Cathodes within Lithium Primary Batteries

For batteries to function effectively all active material must be accessible requiring both electron and ion transport to each particle. A common approach to generating the needed conductive network is the addition of carbon to create a composite electrode. An alternative approach is the electrochemically induced formation of conductive reaction products where the electrochemically generated materials are in intimate contact with the active material contributing to effective connection of each active particle. Furthermore, this study probes silver vanadium oxide (Ag 2 V 4 O 11 , SVO), carbon monofluoride (CF x ), and hybrid SVO/CF x electrodes in lithium batteries. Ex situ XRD identifies Ag 0 as a reduction product from SVO and LiF from CF x that can be followed as a function of depth-of-discharge (DOD). Spatially-resolved operando energy dispersive x-ray diffraction reveals that the presence of SVO alleviates reaction heterogeneity in the electrodes which are electron transfer limited in the absence of sufficient Ag 0 . Synchrotron X-ray tomography on discharged cathodes reveals the distribution of silver particles where the particles are more closely spaced near the current collector indicating multiple nucleation sites for their formation. Finally, operando isothermal microcalorimetry is used to determine the heat dissipation of the parent and hybrid battery types. Using material enthalpy potentials, we determine the current distribution between the two active materials for the discharging hybrid cathode adding further insight to the diffraction analysis. Taken together, these results provide a comprehensive understanding of hybrid SVO/CF x cathodes and give guidance on optimal compositions that balance power and energy density considerations.

36 MATERIALS SCIENCE↗

NASA NTRS1995

Internal and surface phenomena in metal combustion

Combustion of metals has been widely studied in the past, primarily because of their high oxidation enthalpies. A general understanding of metal combustion has been developed based on the recognition of the existence of both vapor-phase and surface reactions and involvement of the reaction products in the ensuing heterogeneous combustion. However, distinct features often observed in metal particle combustion, such as brightness oscillations and jumps (spearpoints), disruptive burning, and non-symmetric flames are not currently understood. Recent metal combustion experiments using uniform high-temperature metal droplets produced by a novel micro-arc technique have indicated that oxygen dissolves in the interior of burning particles of certain metals and that the subsequent transformations of the metal-oxygen solutions into stoichiometric oxides are accompanied with sufficient heat release to cause observed brightness and temperature jumps. Similar oxygen dissolution has been observed in recent experiments on bulk iron combustion but has not been associated with such dramatic effects. This research addresses heterogeneous metal droplet combustion, specifically focusing on oxygen penetration into the burning metal droplets, and its influence on the metal combustion rate, temperature history, and disruptive burning. A unique feature of the experimental approach is the combination of the microgravity environment with a novel micro-arc Generator of Monodispersed Metal Droplets (GEMMED), ensuring repeatable formation and ignition of uniform metal droplets with controllable initial temperature and velocity. The droplet initial temperatures can be adjusted within a wide range from just above the metal melting point, which provides means to ignite droplets instantly upon entering an oxygen containing environment. Initial droplet velocity will be set equal to zero allowing one to organize metal combustion microgravity experiments in a fashion similar to usual microgravity liquid fuel droplet combustion studies. In addition, the internal compositions of rapidly quenched metal particles will be analyzed using SEM technique. Such compositions are similar to those existing during the combustion and provide new insight on metal combustion processes. The results of this experimental work will be used to model the fundamental mechanisms of metal combustion. Preliminary experimental results on Al and Zr particle combustion at normal gravity are discussed here.

Dreizin, Edward L.↗

DOE OSTI2022

Alkaline Modified Solid Oxide Catalysts for Condensation Reactions between Biomolecules

The coupling of oxygenates derived from biomass is critical to the production of sustainable commodity chemicals. However, most current industrial oxygenate condensation processes rely on highly corrosive homogenous basic catalysts. To find greener alternatives, several condensation reactions were screened using a variety of alkaline-doped MgO and MgO-Al2O3 heterogenous catalysts. These include i) the self-condensation of hexanedione to methylcyclopentenone, ii) the self-condensation of methyl ethyl ketone to form C8 or C12 ketones, and iii) the coupling of dimethyl succinate and benzaldehyde. We demonstrate substantial yields for several condensation reactions that typically require homogenous base catalysts

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Electrode Mesoscale as a Collection of Particles: Coupled Electrochemical and Mechanical Analysis of NMC Cathodes

Battery electrodes are composed of polydisperse particles and a porous, composite binder domain. These materials are arranged into a complex mesostructure whose morphology impacts both electrochemical performance and mechanical response. We present image-based, particle-resolved, mesoscale finite element model simulations of coupled electrochemical-mechanical performance on a representative NMC electrode domain. Beyond predicting macroscale quantities such as half-cell voltage and evolving electrical conductivity, studying behaviors on a per-particle and per-surface basis enables performance and material design insights previously unachievable. Voltage losses are primarily attributable to a complex interplay between interfacial charge transfer kinetics, lithium diffusion, and, locally, electrical conductivity. Mesoscale heterogeneities arise from particle polydispersity and lead to material underutilization at high current densities. Particle-particle contacts, however, reduce heterogeneities by enabling lithium diffusion between connected particle groups. While the porous composite binder domain (CBD) may have slower ionic transport and less available area for electrochemical reactions, its high electrical conductivity makes it the preferred reaction site late in electrode discharge. Mesoscale results are favorably compared to both experimental data and macrohomogeneous models. This work enables improvements in materials design by providing a tool for optimization of particle sizes, CBD morphology, and manufacturing conditions.

42 ENGINEERING↗

DOE OSTI2022

A Heterogeneous Palladium Catalyst for the Polymerization of Olefins Prepared by Halide Abstraction Using Surface R 3 Si + Species

The silylium-like surface species [ i Pr 3 Si][(R F O) 3 Al-OSi≡)] activates (N^N)Pd(CH 3 )Cl (N^N=Ar-N=CMeMeC=N-Ar, Ar=2,6-bis(diphenylmethyl)-4-methylbenzene) by chloride ion abstraction to form [(N^N)Pd-CH 3 ][(R F O) 3 Al-OSi≡)] ( 1 ). A combination of FTIR, solid-state NMR spectroscopy, and reactions with CO or vinyl chloride establish that 1 shows similar reactivity patterns as (N^N)Pd(CH 3 )Cl activated with Na[B(Ar F ) 4 ]. Multinuclear 13 C{ 27 Al} RESPDOR and 1 H{ 19 F} S-REDOR experiments are consistent with a weakly coordinated ion-pair between (N^N)Pd-CH 3 + and [(R F O) 3 Al-OSi≡)]. 1 catalyzes the polymerization of ethylene with similar activities as [(N^N)Pd-CH 3 ] + in solution and incorporates up to 0.4% methyl acrylate in copolymerization reactions. 1 produces polymers with significantly higher molecular weight than the solution catalyst, and generates the highest molecular weight polymers currently reported in copolymerization reactions of ethylene and methylacrylate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2026

Enhancing Sensitivity in Targeted Single-Cell Proteomics by Coupling a Dual Ion Funnel Interface with Triple Quadrupole Mass Spectrometer

Single-cell proteomics (SCP) has emerged as a powerful approach for understanding cellular heterogeneity and biological processes at unprecedented resolution. However, the extremely limited protein content of individual cells (femtogram to picogram levels) pushes current mass spectrometry instrumentation to its sensitivity limits, creating a critical analytical bottleneck. While selected reaction monitoring (SRM) using triple quadrupole (QqQ) instruments 1 offers advantages in sensitivity and reproducibility for targeted proteomics quantification, SRM still struggles with sensitivity for quantification of moderate- or low-abundance proteins from single-cell sample amounts. Here, we report the development and systematic evaluation of a dual ion funnel interface designed to address the sensitivity limitation by significantly enhancing ion transmission efficiency in commercial QqQ mass spectrometers. The dual ion funnel interface, composed of a curved S-funnel followed by a conventional ion funnel, improves ion transmission efficiency while reducing chemical noise through selective ion focusing. The performance of the dual ion funnel interface was systematically compared to standard interface on a TSQ Vantage platform across samples with different levels of complexity. The dual funnel interface demonstrated to provide up to 25-fold improvement in sensitivity across a wide range of protein concentrations in different biological matrices (low complex mouse macrophage and high complex human cells). Critically, enhanced sensitivity was accompanied by increased analytical reproducibility with lower coefficient of variations. Most importantly, the dual funnel interface enabled reliable quantification of low-abundance proteins that were barely detectable or not detected by the standard interface, extending analysis to single-cell equivalent amounts while maintaining excellent reproducibility. These results demonstrate that the dual funnel interface addresses the critical bottleneck in quantitative targeted proteomics, providing a technological foundation for ultrasensitive targeted SCP that requires both high sensitivity and robust quantitative performance.

Min, Sehong↗

DOE OSTI2022

Probing multiscale dissolution dynamics in natural rocks through microfluidics and compositional analysis

Mineral dissolution significantly impacts many geological systems. Carbon released by diagenesis, carbon sequestration, and acid injection are examples where geochemical reactions, fluid flow, and solute transport are strongly coupled. The complexity in these systems involves interplay between various mechanisms that operate at timescales ranging from microseconds to years. Current experimental techniques characterize dissolution processes using static images that are acquired with long measurement times and/or low spatial resolution. These limitations prevent direct observation of how dissolution reactions progress within an intact rock with spatially heterogeneous mineralogy and morphology. We utilize microfluidic cells embedded with thin rock samples to visualize dissolution with significant temporal resolution (100 ms) in a large observation window (3 × 3 mm). Here we injected acidic fluid into eight shale samples ranging from 8 to 86 wt % carbonate. The pre- and postreaction microstructures are characterized at the scale of pores (0.1 to 1 µm) and fractures (1 to 1,000 µm). We observe that nonreactive particle exposure, fracture morphology, and loss of rock strength are strongly dependent on both the relative volume of reactive grains and their distribution. Time-resolved images of the rock unveil the spatiotemporal dynamics of dissolution, including two-phase flow effects in real time and illustrate the changes in the fracture interface across the range of compositions. Moreover, the dynamical data provide an approach for characterizing reactivity parameters of natural heterogeneous samples when porous media effects are not negligible. The platform and workflow provide real-time characterization of geochemical reactions and inform various subsurface engineering processes.

58 GEOSCIENCES↗

DOE OSTI2021

Energy catalysis needs ligands with high oxidative stability

Replacing fossil fuel-based energy by renewable sources is a transition that society needs to make to meet future energy demand and simultaneously address climate change. Coupling renewable energy sources with electrochemical catalysis provides a promising path to carbon-neutral fuels and chemicals when the necessary reducing equivalents and protons are harvested from water. Developing highly active, stable, and inexpensive electrocatalysts for the oxygen evolution reaction (OER) is accordingly a centerpiece of a renewable energy portfolio. Whereas viable OER catalysts are heterogeneous in nature, owing to their oxidative stability, the realization of stable molecular OER catalysts greatly expands the horizon of energy science with the ability to tune OER energetics and mechanisms with fidelity. In this perspective, current challenges in the field of molecular OER catalysis are addressed with promising lines of research that are directed to designing ligands that can withstand the harsh oxidizing environment of OER.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Controlling the corrosion resistance of multi-principal element alloys

Multi-principal element alloys (MPEAs) offer the possibility of many degrees of freedom in the choice of alloying elements to produce either single phase solid solutions or more complex multiphase microstructures. Large ranges of material properties have been observed for MPEAs and mastery of the selection of elements and their compositions can enable novel combinations of properties not possible in traditional alloys. From the aqueous corrosion perspective, optimization of phase stability, control of heterogeneities, passive film identity and its protectiveness, as well as substrate properties such as metal-metal bond strength and activation energy associated with dissolution, can all be controlling factors governed by alloy composition and structure. These factors can mediate the electrochemical reactions controlling spontaneous corrosion. The quest for superior properties based on well-informed element choice is suggested as a path forward guiding MPEA formulations for corrosion performance. However, gaps in fundamental knowledge exist regarding (a) the specific functions of each element, (b) the behavior of elements in unusual combinations, and (c) the formation of complex protective oxides. These issues currently hold back progress in optimization of corrosion properties.

Scully, John R.↗

DOE OSTI2025

Precise Synthesis of 4.75 V-Tolerant LiCoO 2 with Homogeneous Delithiation and Reduced Internal Strain

The rapid advancements in 3C electronic devices necessitate an increase in the charge cutoff voltage of LiCoO 2 to unlock a higher energy density that surpasses the currently available levels. However, the structural devastation and electrochemical decay of LiCoO 2 are significantly exacerbated, particularly at ≥4.5 V, due to the stress concentration caused by more severe lattice expansion and shrinkage, coupled with heterogeneous Li + intercalation/deintercalation reactions. Herein, employing the molten-salt synthesis technique, we propose a universal morphology-shaping strategy to attain bulk reaction homogeneity and reduce internal strains, even at extremely high charge voltages. The newly designed flattened polygon prismlike LiCoO 2 (P-LCO) particle, featuring a regular symmetrical arrangement along the c-axis, demonstrates a more homogeneous Li + extraction/insertion reaction, which results in a restrained transformation to detrimental O1 phase and reduced variation in lattice volume throughout the (de)lithiation processes. This benefits the mitigation of the local stress accumulation misfit dislocations and particle cracking, ultimately maintaining the mechanical stability of the cathode. Consequently, P-LCO is capable of breaking the voltage ceiling and exhibits exceptional long-term cycling capability at an ultrahigh voltage of 4.75 V. In conclusion, this work offers a brand-new perspective for the rational design of cathode morphology to address capacity deterioration caused by inhomogeneous delithiation and internal strain, thus inspiring the development of high-energy-density cathodes with improved durability.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Heterogeneous Catalysis by Fullerene C 60 : Photocatalytic Dehydro‐Dimerization of Primary Amines and Tetrahydroquinolines Studied Using Thread Spray Mass Spectrometry

Abstract Removal of a catalyst after a catalytic process is a time‐consuming and challenging process. In this paper, a fullerene catalyst coated on cellulose thread is developed and applied it in a heterogeneous photoreaction screening via a thread spray mass spectrometry (MS) platform. The surface of the cellulose thread is modified with NH 2 groups, which subsequently allows immobilization of fullerene C 60 on the thread. The final fullerene functionalized thread is placed in a glass capillary and the solution of the reactant to be interrogated is added. The assembly of thread and glass capillary is placed in front of a mass spectrometer, which serves as an online photoreaction platform after a light source and direct current high voltage are applied. As an ambient ionization approach, the photocatalytic reaction screening platform enabled real‐time MS characterization of products and intermediates and using only nanomole quantities of reactants. Fullerene C 60 is identified to facilitate dehydro‐dimerization reactions from amines. Norharmane shows a unique photo‐oxygenated dimer formation. The functionalized threads immobilized with fullerene C 60 are reusable, confirming the heterogeneous nature of the platform. Thus, this system provided real‐time screening of reactions catalyzed by fullerene C 60 and a means to investigate the reaction mechanism.

Chemistry↗

DOE OSTI2023

Regulating Li Nucleation and Growth Heterogeneities via Near-Surface Lithium-Ion Irrigation for Stable Anode-Less Lithium Metal Batteries

The inhomogeneous nucleation and growth of Li dendrite combined with the spontaneous side reactions with the electrolytes dramatically challenge the stability and safety of Li metal anode (LMA). Despite tremendous endeavors, current success relies on the use of significant excess of Li to compensate the loss of active Li during cycling. Herein, a near-surface Li + irrigation strategy is developed to regulate the inhomogeneous Li deposition behavior and suppress the consequent side reactions under limited Li excess condition. The conformal polypyrrole (PPy) coating layer on Cu surface via oxidative chemical vapor deposition technique can induce the migration of Li + to the interregional space between PPy and Cu, creating a near-surface Li + -rich region to smooth diffusion of ion flux and uniform the deposition. Moreover, as evidenced by multiscale characterizations including synchrotron high-energy X-ray diffraction scanning, a robust N-rich solid-electrolyte interface (SEI) is formed on the PPy skeleton to effectively suppress the undesired SEI formation/dissolution process. Strikingly, stable Li metal cycling performance under a high areal capacity of 10 mAh cm -2 at 2.0 mA cm -2 with merely 0.5 × Li excess is achieved. The findings not only resolve the long-standing poor LMA stability/safety issues, but also deepen the mechanism understanding of Li deposition process.

25 ENERGY STORAGE↗

DOE OSTI2020

Reaction heterogeneity in practical high-energy lithium–sulfur pouch cells

The lithium–sulfur (Li–S) battery is a promising next-generation energy storage technology because of its high theoretical energy and low cost. Extensive research efforts have been made on new materials and advanced characterization techniques for mechanistic studies. However, it is uncertain how discoveries made on the material level apply to realistic batteries due to limited analysis and characterization of real high-energy cells, such as pouch cells. Evaluation of pouch cells (>1 A h) (instead of coin cells) that are scalable to practical cells provides a critical understanding of current limitations which enables the proposal of strategies and solutions for further performance improvement. Herein, we design and fabricate pouch cells over 300 W h kg -1 , compare the cell parameters required for high-energy pouch cells, and investigate the reaction processes and their correlation to cell cycling behavior and failure mechanisms. Spatially resolved characterization techniques and fluid-flow simulation reveal the impacts of the liquid electrolyte diffusion within the pouch cells. We found that catastrophic failure of high-energy Li–S pouch cells results from uneven sulfur/polysulfide reactions and electrolyte depletion for the first tens of cycles, rather than sulfur dissolution as commonly reported in the literature. The uneven reaction stems from limited electrolyte diffusion through the porous channels into the central part of thick cathodes during cycling, which is amplified both across the sulfur electrodes and within the same electrode plane. A combination of strategies is suggested to increase sulfur utilization, improve nanoarchitectures for electrolyte diffusion and reduce consumption of the electrolytes and additives.

25 ENERGY STORAGE↗

NASA NTRS2003

Uptake of Small Organic Compounds by Sulfuric Acid Aerosols: Dissolution and Reaction

To assess the role of oxygenated volatile organic compounds in the upper troposphere and lower stratosphere, the interactions of a series of small organic compounds with low-temperature aqueous sulfuric acid will be evaluated. The total amount of organic material which may be taken up from the gas phase by dissolution, surface layer formation, and reaction during the particle lifetime will be quantified. Our current results for acetaldehyde uptake on 40 - 80 wt% sulfuric acid solutions will be compared to those of methanol, formaldehyde, and acetone to investigate the relationships between chemical functionality and heterogeneous activity. Where possible, equilibrium uptake will be ascribed to component pathways (hydration, protonation, etc.) to facilitate evaluation of other species not yet studied in low temperature aqueous sulfuric acid.

Iraci, L. T.↗

NASA NTRS1999

Heterogeneous Combustion of Porous Graphite Particles in Normal and Microgravity

Combustion of solid fuel particles has many important applications, including power generation and space propulsion systems. The current models available for describing the combustion process of these particles, especially porous solid particles, include various simplifying approximations. One of the most limiting approximations is the lumping of the physical properties of the porous fuel with the heterogeneous chemical reaction rate constants. The primary objective of the present work is to develop a rigorous model that could decouple such physical and chemical effects from the global heterogeneous reaction rates. For the purpose of validating this model, experiments with porous graphite particles of varying sizes and porosity are being performed at NASA Lewis Research Center. The details of the experimental and theoretical model development effort are described.

Chelliah, Harsha↗