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DOE OSTI2026

Deciphering competing elementary steps to correlate electrocatalyst chemical state with activity

The overpotential in multielectron transfer heterogeneous electrocatalysis fundamentally arises from thermodynamic and kinetic disparities among elementary steps; however, deciphering coupled and competing steps has long remained a challenge. Here, we establish an electrochemical deconvolution paradigm based on key processes in electrocatalytic reactions, such as charge accumulation, electron/proton transfer, and intermediate evolution, to resolve competing elementary steps. Taking the oxygen evolution reaction as a prototypical reaction, we design a model catalyst featuring a precise isolated cation-anion vacancy pair and track the previously elusive electrochemical behavior of lattice oxygen by disentangling interference from adsorbed oxygen intermediates. Mechanistically, the lattice oxygen oxidation pathway originates from the spontaneous, nonelectrochemical deprotonation of replenished water molecules coordinated to unsaturated cation sites. Alternating current techniques further reveal that although lattice oxygen oxidation requires a higher potential than metal oxidation, it exhibits faster kinetics, providing insight into its superior catalytic activity. These findings establish a direct experimental correlation between the initial chemical state and the catalytic activity and prove surface-confined lattice oxygen cycling. Furthermore, expanding conventional potential-current analysis into a multidimensional framework enables disentanglement of thermodynamic and kinetic contributions of key elementary steps, thereby guiding the rational optimization of various complex multielectron transfer reactions.

OER↗

DOE OSTI2023

Advanced Algal Biofoundries for the Production of Polyurethane Precursors

The primary goal of the BEEPs project was to develop a process that could accelerate the development of algae as bioproduction platforms, from initial chemical product concept to an economically viable market supply. Under this program we elected to develop strains of algae that could generate polyurethane precursors, while simultaneously developing basic genetic tools to enable improved algal production systems. This program was specifically designed to incorporate National Laboratories as a means to utilize the expertise and facilities for new bio-production platforms. To that end, we designed a program to collaborate with the Agile BioFoundry at Lawrence Berkeley National Laboratory (LBNL) and computational platforms at Pacific Northwest National Laboratory (PNNL). In addition to these National Laboratory partners, we also had academic partners from UC Davis and Georgia Tech, as well as commercial partners Algenesis Materials and BASF. To achieve these goals, we initially focused on developing the genetic tools and high throughput screening technologies necessary to generate and assess production of polymer precursors (succinic acid) in algae and cyanobacteria, including advanced promoters and biosensors. In parallel, we computationally identified potential production bottlenecks and then used the developed genetic tools to increase production rates and yields. Constant feedback of data was used in conjunction with machine learning, high-throughput cell sorting, and synthetic biology, for additional targeted metabolic engineering. Multiple rounds of tool design, building, testing, and learning were supplied to partners at PNNL and LBNL to develop new models and tools that could expedite bioproduction platform development and increase yield performance. We targeted, and achieved, the FOA requirement yield metric of 20 g/L, as a milestone and deliverable from at least one of our engineered strains for the production of succinic acid.

09 BIOMASS FUELS↗

NASA NTRS2011

On the Effect of Dust Particles on Global Cloud Condensation Nuclei and Cloud Droplet Number

Aerosol-cloud interaction studies to date consider aerosol with a substantial fraction of soluble material as the sole source of cloud condensation nuclei (CCN). Emerging evidence suggests that mineral dust can act as good CCN through water adsorption onto the surface of particles. This study provides a first assessment of the contribution of insoluble dust to global CCN and cloud droplet number concentration (CDNC). Simulations are carried out with the NASA Global Modeling Initiative chemical transport model with an online aerosol simulation, considering emissions from fossil fuel, biomass burning, marine, and dust sources. CDNC is calculated online and explicitly considers the competition of soluble and insoluble CCN for water vapor. The predicted annual average contribution of insoluble mineral dust to CCN and CDNC in cloud-forming areas is up to 40 and 23.8%, respectively. Sensitivity tests suggest that uncertainties in dust size distribution and water adsorption parameters modulate the contribution of mineral dust to CDNC by 23 and 56%, respectively. Coating of dust by hygroscopic salts during the atmospheric aging causes a twofold enhancement of the dust contribution to CCN; the aged dust, however, can substantially deplete in-cloud supersaturation during the initial stages of cloud formation and can eventually reduce CDNC. Considering the hydrophilicity from adsorption and hygroscopicity from solute is required to comprehensively capture the dust-warm cloud interactions. The framework presented here addresses this need and can be easily integrated in atmospheric models.

Karydis, V. A.↗

DOE OSTI2022

Probing topological phase transitions using high-harmonic generation

We report the prediction and realization of topological insulators have sparked great interest in experimental approaches to the classification of materials. The phase transition between non-trivial and trivial topological states is important, not only for basic materials science but also for next-generation technology, such as dissipation-free electronics. It is therefore crucial to develop advanced probes that are suitable for a wide range of samples and environments. Here we demonstrate that circularly polarized laser-field-driven high-harmonic generation is distinctly sensitive to the non-trivial and trivial topological phases in the prototypical three-dimensional topological insulator bismuth selenide. The phase transition is chemically initiated by reducing the spin–orbit interaction strength through the substitution of bismuth with indium atoms. We find strikingly different high-harmonic responses of trivial and non-trivial topological surface states that manifest themselves as a conversion efficiency and elliptical dichroism that depend both on the driving laser ellipticity and the crystal orientation. The origins of the anomalous high-harmonic response are corroborated by calculations using the semiconductor optical Bloch equations with pairs of surface and bulk bands. As a purely optical approach, this method offers sensitivity to the electronic structure of the material, including its nonlinear response, and is compatible with a wide range of samples and sample environments.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2023

Decorrelated singlet and triplet exciton delocalization in acetylene-bridged Zn-porphyrin dimers

The controlled delocalization of molecular excitons remains an important goal towards the application of organic chromophores in processes ranging from light-initiated chemical transformations to classical and quantum information processing. In this study, we present a methodology to couple optical and magnetic spectroscopic techniques and assess the delocalization of singlet and triplet excitons in model molecular chromophores. By comparing the steady-state and time-resolved optical spectra of Zn-porphyrin monomers and weakly coupled dimers, we show that we can use the identity of substituents bound at specific positions of the macromolecules' rings to control the inter-ring delocalization of singlet excitons stemming from their B states through acetylene bridges. While broadened steady-state absorption spectra suggest the presence of delocalized B state excitons in mesityl-substituted Zn-tetraphenyl porphyrin dimers (Zn 2 U-D), we confirm this conclusion by measuring an enhanced ultrafast non-radiative relaxation from these inter-ring excitonic states to lower lying electronic states relative to their monomer. In contrast to the delocalized nature of singlet excitons, we use time-resolved EPR and ENDOR spectroscopies to show that the triplet states of the Zn-porphyrin dimers remain localized on one of the two macrocyclic sub-units. We use the analysis of EPR and ENDOR measurements on unmetallated model porphyrin monomers and dimers to support this conclusion. The results of DFT calculations also support the interpretation of localized triplet states. These results demonstrate researchers cannot conclude triplet excitons delocalize in macromolecular based on the presence of spatially extended singlet excitons, which can help in the design of chromophores for application in spin conversion and information processing technologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Instrumentation and methods for efficient time-resolved X-ray crystallography of biomolecular systems with sub-10 ms time resolution

Time-resolved X-ray crystallography has great promise to illuminate structure–function relations and key steps of enzymatic reactions with atomic resolution. The dominant methods for chemically-initiated reactions require complex instrumentation at the X-ray beamline, significant effort to operate and maintain this instrumentation, and enormous numbers (∼10 5 –10 9 ) of crystals per time point. We describe instrumentation and methods that enable high-throughput time-resolved study of biomolecular systems using standard crystallography sample supports and mail-in X-ray data collection at standard high-throughput cryocrystallography synchrotron beamlines. The instrumentation allows rapid reaction initiation by mixing of crystals and substrate/ligand solution, rapid capture of structural states via thermal quenching with no pre-cooling perturbations, and yields time resolutions in the single-millisecond range, comparable to the best achieved by any non-photo-initiated method in both crystallography and cryo-electron microscopy. Our approach to reaction initiation has the advantages of simplicity, robustness, low cost, adaptability to diverse ligand solutions and small minimum volume requirements, making it well suited to routine laboratory use and to high-throughput screening. We report the detailed characterization of instrument performance, present structures of binding of N -acetylglucosamine to lysozyme at time points from 8 ms to 2 s determined using only one crystal per time point, and discuss additional improvements that will push time resolution toward 1 ms.

Indergaard, John A. (ORCID:000000022367699X)↗

DOE OSTI2024

Advanced Algal Biofoundries for the Production of Polyurethane Precursors (CRADA Final Report)

09 BIOMASS FUELS↗

DOE OSTI2026

Detailed Method for the Purification of Rhamnogalacturonan-I (RG-I) in Arabidopsis thaliana

The plant cell wall is a dynamic and complex extracellular matrix that not only provides structural integrity and determines cell shape but also mediates intercellular communication. Among its major components, pectins play essential roles in cell adhesion, wall porosity, hydration, and flexibility. Rhamnogalacturonan-I (RG-I), a structurally diverse pectic polysaccharide, remains one of the least understood components of the plant cell wall. Its backbone is substituted with arabinan, galactan, and arabinogalactan side chains that vary in length, branching, and composition across tissues, species, and developmental stages. In addition, RG-I can undergo modifications such as backbone acetylation, further contributing to its structural complexity and functional diversity. To advance understanding of RG-I, we present a detailed method for isolating RG-I from the model plant Arabidopsis thaliana . Leveraging Arabidopsis as a model system provides major advantages owing to its well-characterized genome and powerful molecular toolkit, enabling deeper investigation into the roles of RG-I in plant development and responses to environmental stress. Our method consists of two major steps: an initial chemical extraction using oxalate, followed by endo-polygalacturonase (EPG) digestion to fragment the pectic domains. An advantage of this approach is that it produces a dry material that can be stored at room temperature without special handling and does not introduce chemicals that may interfere with downstream analyses. The purified RG-I can be used for detailed compositional and structural analyses, as well as for functional studies of enzymes involved in pectin biosynthesis, modification, and degradation. Although this protocol was developed for isolating RG-I from Arabidopsis rosette leaves, it is also applicable to other Arabidopsis organs and other plant species.

25 ENERGY STORAGE↗

NASA NTRS1974

Studies of aircraft wake chemistry and dispersion

Use of aerospace technology to study aircraft wakes is reviewed. It is shown how aerospace vehicles can be used to provide data for increased understanding of the atmosphere and of aircraft exhaust trails where knowledge is inadequate to evaluate fully the potential impact of the engine emissions. Models of aircraft near-field exhaust wakes are characterized by jet, vortex, and dispersion regimes. Wake growth in the jet regime is self-determined and rapid, whereas further spreading is inhibited in the vortex regime because of circulating vortex motion. Wake diffusion in the dispersion regime is initially influenced by aircraft induced turbulence but is dominated later by small-scale atmospheric turbulence. Computed fluid mechanical results show the importance of effects such as wake buoyancy, wind shear, turbulence, and traffic corridor exhaust buildup on dispersion of the wake. In the jet regime the exhaust characteristics and thermochemistry serve to illustrate initial chemical changes involving potential pollutant species.

Poppoff, I. G.↗

NASA NTRS1976

Stellar evolution at high mass with semiconvective mixing according to the Schwarzschild criterion

Evolutionary sequences for stellar models with 10, 15, 30, and 60 solar masses, as well as four different initial chemical compositions, are calculated to the end of core helium burning using the Schwarzschild criterion for convection. The results are analyzed in terms of the modifications of interior structure and surface parameters induced by semiconvective mixing as a result of adopting the Schwarzschild criterion. It is found that the main differences from results based on the Ledoux criterion are the great extent of the convectively unstable layers in the intermediate zone and the eventual development of a fully convective zone at the base of the semiconvective one. It is shown that semiconvection develops outside the convective core just after the ZAMS stage for masses greater than 12 solar masses and just before the stage of central hydrogen exhaustion for masses greater than 6 solar masses. The present models are found to be insufficiently hot in comparison with the bulk of observed stable blue supergiants and to predict far too many red supergiants fro the range above 20 solar masses. It is concluded that something is fundamentally wrong with the models, the most likely suspects being the stellar opacities adopted and the neglect of mass loss.

Stothers, R.↗

NASA NTRS1977

Heterogeneous chemical reactions: Preparation of monodisperse latexes

It is demonstrated that a photoinitiated emulsion polymerization can be carried out to a significant conversion in a SPAR rocket prototype polymerization vessel within the six minutes allowed for the experiment. The percentage of conversion was determined by both dilatometry and gravimetric methods with good agreement. The experimental results lead to the following conclusions: (1) emulsion polymerizations can be carried out to conversions as high as 75%, using a stable micellized styrene-SLS system plus photoinitiator; (2) dilatometry can be used to accurately determine both the rate and conversion of polymerization; (3) thermal expansion due to the light source and heat of reaction is small and can be corrected for if necessary; (4) although seeded emulsion polymerizations are unfavorable in photoinitiation, as opposed to chemical initiation, polymerizations can be carried out to at least 15% conversion using 7940A seed particles, with 0.05% solids; and (5) photoinitiation should be used to initiate polymerization in the SPAR rocket experiments because of the mechanical simplicity of the experiment.

Vanderhoff, J. W.↗

NASA NTRS1984

Suboxic diagenesis in banded iron formations

Anomalous isotopic composition has been reported for the carbon in carbonate minerals of banded iron formations. Well studied examples show an enrichment in the light isotope of carbon, C-12. This enrichment presumably reflects unusual circumstances in the deposition of these sedimentary rocks. It is suggested here that the isotopically light carbonate results from early diagenetic oxidation by bacteria of substantial amounts of isotopically light organic carbon. The electron acceptor that permits oxidation in the absence of free oxygen is presumed to be Fe(III), which may have been significantly more abundant in the initial chemical precipitate than in the postdiagenetic sedimentary rock.

Walker, J. C. G.↗

NASA NTRS1989

Properties of mantles on cometary nuclei

The formation, structure, and properties of dusty mantles on cometary nuclei are investigated using various theoretical arguments and experimental data. It is shown how the growth of the mantle is affected by the varying thermal conductivity and how an initial chemically undifferentiated surface layer changes into a mechanically rather weak, less than 10 to the 7th dyn /sq cm, mantle which then strengthens to reach values of the order of 10 to the 8th dyn/sq cm. Organic CHON decomposition products may lower the porosity below the expected value of about 0.5 and lead to an increase of the surface temperature. They may also further strengthen the overall bonding of the mantle.

Smoluchowski, R.↗

NASA NTRS1990

Measurement of the absolute solar UV irradiance and variability

Radiation in the wavelength interval 150-350 nm initiates chemical reactions in the lower mesosphere and the stratosphere through the photodissociation of ambient molecular species. This experiment measures the total solar irradiance, above the Earth's atmosphere, in this wavelength interval, using three spectrometers. Measurements are made from rockets on a once-a-year basis and are used with satellite observations to determine both the absolute irradiance and the long term variability of the sun in the UV. A fourth spectrometer is being added to the payload to measure the emission in the hydrogen Lyman-alpha emission at 121.67 nm.

Mentall, James E.↗

NASA NTRS1992

Magma ocean formation due to giant impacts

The effect of giant impacts on the initial chemical and thermal states of the terrestrial planets is just now being explored. A large high speed impact creates an approximately hemispherical melt region with a radius that depends on the projectile's radius and impact speed. It is shown that giant impacts on large planets can create large, intact melt regions containing melt volumes up to a few times the volume of the projectile. These large melt regions are not created on asteroid sized bodies. If extruded to the surface, these regions contain enough melt to create a magma ocean of considerable depth, depending on the impact speed, projectile radius, and gravity of the target planet.

Tonks, W. B.↗

NASA NTRS1994

On the X-ray spectrum of Kepler's supernova remnant

We have devised a method to do nonequilibrium ionization calculations on the results of two-dimensional hydrodynamical simulations, based on the algorithm of Hughes & Helfand (1985). We have calculated the ionization structure and X-ray emission for a two-dimensional numerical hydrodynamical simulation for the remnant of Kepler's supernova (SN); the hydrodynamical model was presented in a previous paper. In this model, the progenitor of Kepler's SN is assumed to have been a massive runaway star ejected from the Galactic plane. In its red supergiant stage, its dense stellar wind was distorted and compressed into a bow shock by the ram pressure of the tenuous interstellar medium. The subsequent interaction of the supernova ejecta with this asymmetric circumstellar matter produced a strongly asymmetric supernova remnant (SNR). In this paper, we present calculated X-ray spectra for this hydrodynamical model. A comparison with observations implies a moderate overabundance of Fe in Kepler's SNR (only 50% larger than its cosmic value), in contrast to a large (6 to 15) Fe overabundance derived previously. However, we confirm earlier conclusions that Si and S abundances are 2 to 3 times solar. These modest enhancements of Si, S, and Fe may be attributed either to heavy-element enriched SN ejecta or to the initial chemical abundances of the SN progenitor, which originated in the metal-rich inner Galaxy. The comparison of our models with the observed spectra confirm theoretical predictions that moderate electron heating occurs at strong collisionless shock fronts, with the implied electron/mean temperature ratio of approximately 0.5.

Borkowski, Kazimierz J.↗

NASA NTRS2003

Magnetogasdynamic Power Extraction and Flow Conditioning for a Gas Turbine

An extension of the Russian AJAX concept to a turbojet is being explored. This magnetohydrodynamic (MHD) energy bypass engine cycle incorporating conventional gas turbine technology has MHD flow conditioning at the inlet to electromagnetically extract part of the inlet air kinetic energy. The electrical power generated can be used for various on-board vehicle requirements including plasma flow control around the vehicle or it may be used for augmenting the expanding flow in the high speed nozzle by MHD forces to generate more thrust. In order to achieve this interaction, the air needs to be ionized by an external means even up to fairly high flight speeds, and the leading candidates may be classified as electrical discharge devices. The present kinetic modeling calculations suggest that the use of electron beams with characteristics close to the commercially available e-beam systems (electron energy approx. 60 keV, beam current approx. 0.2 mA/sq cm) to sustain ionization in intermediate pressure, low-temperature (P = 0.1 atm, T = 300 K) supersonic air flows allows considerable reduction of the flow kinetic energy (up to 10 to 20 percent in M = 3 flows). The calculations also suggest that this can be achieved at a reasonable electron beam efficiency (eta approx. 5), even if the e-beam window losses are taken into account. At these conditions, the exit NO and O atom concentrations due to e-beam initiated chemical reactions do not exceed 30 ppm. Increasing the beam current up to approx. 2 mA/sq cm, which corresponds to a maximum electrical conductivity of sigma(sub max) approx. 0.8 mho/m at the loading parameter of K = 0.5, would result in a much greater reduction of the flow kinetic energy (up to 30 to 40 percent). The MHD channel efficiency at these conditions would be greatly reduced (to eta approx. 1) due to increased electron recombination losses in the channel. At these conditions, partial energy conversion from kinetic energy to heat would result in a significant total pressure loss (P(sub 0)/P(sub 0i) approx. 0.3). The total pressure loss can be reduced operating at the loading parameter closer to unity, at the expense of the reduced electrical power output. Raising the beam current would also result in the increase of the exit O atom concentrations (up to 600 ppm) and NO (up to 150 ppm).

Adamovich, Igor V.↗

NASA NTRS2006

The Carbon Monoxide Tape Recorder

Using Aura MLS data we have identified the stratospheric tape recorder in carbon monoxide (CO). Unlike the water vapor tape recorder, which is controlled by upper troposphere processes, the CO tape recorder is linked to seasonal biomass burning. Since CO has a lifetime of only a few months, the CO tape recorder barely extends above 20 km. The tape head for CO appears to be close to 360K near the same location as the water vapor tape head [Read et al, 20041. Both tape heads are below the equatorial cold point tropopause but above the base of the tropical tropopause layer. The tape recorder signal becomes more distinct from 360K to 380K suggesting that convective detrainment of plays a decreasingly important role with altitude. The Global Modeling Initiative chemical transport model forced by the climatology of biomass burning reproduces the CO tape recorder.

Schoeberl, M. R.↗