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All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Two Artificial Leaf Architectures for Solar Formate Production From CO 2 and H 2 O

Sunlight-powered artificial leaves for the production of formate from CO 2 are an attractive route to solar fuels, yet existing solar formate devices remain low in performance, and their architecture and material choices are underexplored. Herein, we report the fabrication of two distinct fully integrated, self-standing solar formate device architectures and elucidate the underlying design principles and material selection strategies. The first architecture integrates a Si photocathode with a BiVO 4 photoanode and utilizes a highly active Pd catalyst for CO 2 reduction. It represents the first artificial leaf device comprising two photoelectrodes (excluding photovoltaic [PV]-biased electrodes) for effective formate production under single-beam illumination. The second architecture employs a dark cathode and a dark anode driven by a 4-junction perovskite solar cell and uses a highly stable Bi catalyst for CO 2 reduction. This device delivers a record-high formate production rate of 174 µmol h −1 with a remarkable solar-to-formate energy efficiency of 2% among all artificial leaf devices reported to date. Finally, these results demonstrate the feasibility and outline the design principles of both PV-free and PV-assisted device architectures in solar fuel production.

electrocatalysis↗
DOE OSTI2022

Orographic enhancement of rainfall over the Congo Basin

Abstract The Congo rainforest located in central equatorial Africa is an important, yet understudied part of the globe surrounded by complex orographic features. A primitive understanding of precipitation processes such as mesoscale convective dynamics magnifies uncertainties in the future climate projections of the hydrological cycle over the Congo. Furthermore, the effects of orography, which is an important forcing for convection and precipitation, are poorly resolved by climate models, and ill‐conceptualized over the Congo. To address this knowledge gap, perturbed orographic forcing experiments are conducted using the Weather Research and Forecasting (WRF) mesoscale numerical model in a high‐resolution convection‐permitting model setup. The model simulated selected dates in November 2014. The thunderstorms and rainfall simulated in the control run for the case study analyzed in this article compared reasonably well to satellite‐derived brightness temperature and rainfall data. The results from this case study show that the dynamical impact of increasing the height of the East African Highlands is the blocking of the lower‐tropospheric tropical easterlies. This weakening of the lower‐tropospheric zonal winds increases the windshear over the Congo Basin resulting in slower propagating, more intense mesoscale convective systems with enhanced rainfall.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Characterizing the Impact of Oligomerization on Redox Flow Cell Performance

Abstract Redox flow batteries (RFBs) are hindered by complex failure modes, particularly crossover through the membrane, resulting in capacity fade and reduced cycling efficiencies. Redox‐active oligomers (RAOs) have recently been proposed for mitigating this phenomenon while maintaining sufficient transport properties; however, to date, few studies have quantified how the chemical and electrochemical properties of RAOs influence their performance in redox flow cells. Here, we demonstrate that oligomeric derivatives of 2,2,6,6‐tetramethylpiperidine 1‐oxyl (TEMPO) exhibit lower diffusivities than the monomeric species but retain facile charge transfer characteristics. The size‐dependent variations in mass transport rates directly translate to differences in flow cell polarization and symmetric cycling performance. Post‐mortem analyses reveal that oligomerization does not meaningfully alter decay processes as evinced by similar capacity fade across all species. Broadly, these findings corroborate and extend upon previously developed relationships between molecular size, electrochemical properties, and flow cell performance.

36 MATERIALS SCIENCE↗
DOE OSTI2021

3D printing of lignin: Challenges, opportunities and roads onward

Abstract As the second most abundant biopolymer on earth, and as a resource recently becoming more available in separated and purified form on an industrial scale due to the development of new isolation technologies, lignin has a key role to play in transitioning our material industry towards sustainability. Additive manufacturing (AM), the most efficient‐material processing technology to date, has likewise made great strides to promote sustainable industrial solutions to our needs in engineered products. Bringing lignin research to AM has prompted the emergence of the nascent “lignin 3D printing” field. This review presents the recent state of art of this promising field and highlights its challenges and opportunities. Following a review of the industrial availability, molecular attributes, and associated properties of technical lignins, we review R&D efforts at implementing lignin systems in extrusion‐based and stereolithography (SLA) printing technologies. Doing so underlines the adage of lignin research that “all lignins are not created equal,” and stresses the opportunity nested in this chemical diversity created mostly by differences in isolation conditions to molecularly select and tune the attributes of technical lignin systems towards desirable properties, be it by modification or polymer blending. Considering the AM design process in its entirety, we finally propose onward routes to bring the full potential to this emerging field. We hope that this review can help promote the unique value and overdue industrial role of lignin in sustainable engineered materials and products.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Integrative teaching of metabolic modeling and flux analysis with interactive python modules

Abstract The modeling of rates of biochemical reactions—fluxes—in metabolic networks is widely used for both basic biological research and biotechnological applications. A number of different modeling methods have been developed to estimate and predict fluxes, including kinetic and constraint‐based (Metabolic Flux Analysis and flux balance analysis) approaches. Although different resources exist for teaching these methods individually, to‐date no resources have been developed to teach these approaches in an integrative way that equips learners with an understanding of each modeling paradigm, how they relate to one another, and the information that can be gleaned from each. We have developed a series of modeling simulations in Python to teach kinetic modeling, metabolic control analysis, 13C‐metabolic flux analysis, and flux balance analysis. These simulations are presented in a series of interactive notebooks with guided lesson plans and associated lecture notes. Learners assimilate key principles using models of simple metabolic networks by running simulations, generating and using data, and making and validating predictions about the effects of modifying model parameters. We used these simulations as the hands‐on computer laboratory component of a four‐day metabolic modeling workshop and participant survey results showed improvements in learners' self‐assessed competence and confidence in understanding and applying metabolic modeling techniques after having attended the workshop. The resources provided can be incorporated in their entirety or individually into courses and workshops on bioengineering and metabolic modeling at the undergraduate, graduate, or postgraduate level.

Kaste, Joshua A. M.↗
DOE OSTI2021

New Opportunity for Carbon-Supported Ni-based Electrocatalysts: Gas-Phase CO 2 Methanation

The cost-effectiveness and excellent performance of conductive-carbon-supported Ni-based electrocatalysts make them attractive materials for hydrogen oxidation and evolution reactions. However, they were previously unused in gas-phase hydrogenation reactions. In this work, we have expanded the applicability of commercially available advanced Ni/C, NiMo/C and NiRe/C materials from electrocatalysis to heterogeneous catalysis of CO 2 methanation. Our catalytic testing efforts indicate that the monometallic Ni/C material demonstrates the best CO 2 methanation properties, achieving an excellent CO 2 conversion of 83 % at 400 °C with nearly complete selectivity to CH 4 of 99.7 %, plus exhibiting intact performance during 90 h of time-on-stream testing. Such catalytic properties are among the highest reported to date among carbon-supported Ni-based methanation catalysts. Finally, excellent performance of Ni/C stems from the good dispersion of the Ni nanoparticles over N-containing carbon support material.

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

Modulating Transition Metal Reactivity with Force

The reactivity and selectivity of a transition metal catalyst is intimately related to its ligand-sphere geometry, and, in many cases, the ideal ligand geometry for one step of a catalytic cycle is poorly matched to the ideal ligand geometry for another. For this reason, methods for reversibly modulating ligand geometry on the time scale of catalytic turnover or monomer enchainment are highly desirable. Mechanical force represents a heretofore untapped approach to modulate catalyst geometry and/or reactivity, with the potential to do so on the timescale of catalytic turnover or monomer enchainment. Macroscopic mechanical forces are large, directional and localized to an extent that differentiates them from other forms of energy input such as heat or light. Here, in this Concept, we describe our efforts to address the fundamental challenges associated with force-modulated transition metal catalysis by employing molecular force probe ligands comprising a stiff stilbene photoswitch tethered to rotationally flexible biaryl bisphosphine ligand. Our efforts to date include the modulation of catalytic activity through force-mediated ligand perturbations, quantification of the force-coupled ligand effects on the energetics of elementary organometallic transformations, and evaluation of the mechanisms of force transduction in these systems.

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

A One‐Pot Biocatalytic Cascade to Access Diverse l ‐Phenylalanine Derivatives from Aldehydes or Carboxylic Acids

Abstract Nonstandard amino acids (nsAAs) that are l ‐phenylalanine derivatives with aryl ring functionalization have long been harnessed in natural product synthesis, therapeutic peptide synthesis, and diverse applications of genetic code expansion. Yet, to date, these chiral molecules have often been the products of poorly enantioselective and environmentally harsh organic synthesis routes. Here, we reveal the broad specificity of multiple natural pyridoxal 5′‐phosphate (PLP)‐dependent enzymes, specifically an l ‐threonine transaldolase, a phenylserine dehydratase, and an aminotransferase, toward substrates that contain aryl side chains with diverse substitutions. We exploit this tolerance to construct a one‐pot biocatalytic cascade that achieves high‐yield synthesis of 18 diverse l ‐phenylalanine derivatives from aldehydes under mild aqueous reaction conditions. We demonstrate the addition of a carboxylic acid reductase module to this cascade to enable the biosynthesis of l ‐phenylalanine derivatives from carboxylic acids that may be less expensive or less reactive than the corresponding aldehydes. Finally, we investigate the scalability of the cascade by developing a lysate‐based route for preparative‐scale synthesis of 4‐formyl‐ l ‐phenylalanine, a nsAA with a bio‐orthogonal handle that is not readily market‐accessible. Overall, this work offers an efficient, versatile, and scalable route with the potential to lower manufacturing costs and democratize synthesis for many valuable nsAAs.

Anderson, Shelby R. [Department of Chemical and Bi↗
DOE OSTI2020

Microstructural and chemical characterization of a purple pigment from a Faiyum mummy portrait

Results are presented from analyses that were conducted to explain the presence of chromium, detected noninvasively using energy dispersive X-ray fluorescence (XRF), in the unusually large (2-3mm diameter) rough gem-like purple pigment particles in the paint used for a Faiyum mummy portrait. An approximately 50 µm diameter particle of the chromium-containing purple pigment was extracted from the Portrait of a Bearded Man, dated to Roman Imperial Egypt in the second century, circa 170-180 CE, accession #32.6 in the Walters Art Museum collection. The particle was characterized using energy dispersive X-ray fluorescence analysis, electron microscopy, diffraction, and atom probe tomography. It is demonstrated that the purple pigment particle is a heterogeneous organic pigment, specifically, a lake pigment likely derived from either plant or insect matter, which contains minor percentages of both transition metals and alkali / alkali earth metals, with nanometer-scale crystallites of lead carbonates and sulfates. The analyses revealed for the first time the nanoscale microstructure and stratigraphy in an ancient lake pigment. Results suggest that similarities with respect to time-period and place of production may be developed among unprovenienced Faiyum mummy portraits to help localize workshops or artists, using analyses focused on lake pigments to characterize specifically metal-based mordants.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Probing Basal and Prismatic Planes of Graphitic Materials for Metal Single Atom and Subnanometer Cluster Stabilization

Abstract Supported metal single atom catalysis is a dynamic research area in catalysis science combining the advantages of homogeneous and heterogeneous catalysis. Understanding the interactions between metal single atoms and the support constitutes a challenge facing the development of such catalysts, since these interactions are essential in optimizing the catalytic performance. For conventional carbon supports, two types of surfaces can contribute to single atom stabilization: the basal planes and the prismatic surface; both of which can be decorated by defects and surface oxygen groups. To date, most studies on carbon‐supported single atom catalysts focused on nitrogen‐doped carbons, which, unlike classic carbon materials, have a fairly well‐defined chemical environment. Herein we report the synthesis, characterization and modeling of rhodium single atom catalysts supported on carbon materials presenting distinct concentrations of surface oxygen groups and basal/prismatic surface area. The influence of these parameters on the speciation of the Rh species, their coordination and ultimately on their catalytic performance in hydrogenation and hydroformylation reactions is analyzed. The results obtained show that catalysis itself is an interesting tool for the fine characterization of these materials, for which the detection of small quantities of metal clusters remains a challenge, even when combining several cutting‐edge analytical methods.

Vidal, Mathieu↗
DOE OSTI2025

Designing Cyclic Nitrogen‐Bridged Sulfonamides with Anti‐Cancer Activity

The N-bridgehead heterocyclic structure is an abundant motif in a multitude of natural products. This structural feature is of high interest because it is present in many different bioactive molecules, many of which are well-established pharmaceuticals. The introduction of a sulfone group into the N-bridgehead system yields a new core structure containing a N-bridgehead sulfonamide. While linear sulfonamides can be found in natural products, only artificial cyclic sulfonamides are known to date. Applications of related cyclic sulfonamide compounds include matrix metalloproteinase inhibitors, potential HIV and cancer therapeutics, and anti-inflammatory compounds. To explore the potential bioactivity of the N-bridgehead sulfonamide scaffold, a synthetic route toward these scaffolds is developed and their bioactivity is explored against different cancer cell lines.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2020

A Systematic Assessment of US Food and Drug Administration Dosing Recommendations For Drug Development Programs Amenable to Response‐Guided Titration

A key goal in drug development is optimized dosing for patients. Interactions between drug developers and regulatory scientists throughout development are important for the optimization of dosing and serve as a forum to discuss approaches for optimal dosing, such as precision or individualized dosing. To date, there has not been a systematic assessment of the advice provided by the US Food and Drug Administration (FDA) to drug developers from an individualized dosing perspective. Here, we reviewed FDA recommendations on dose selection for efficacy trials at end‐of‐phase meetings between the FDA and drug developers for 76 new molecular entities approved between 2013 and 2017 that are considered amenable for an individualized dosing method, response‐guided titration. Forty FDA dosing recommendations were identified as specific to dose selection and design of the respective efficacy trials and subsequently: (i) characterized based on if they were supportive of individualized dosing and (ii) compared with dosing regimens used in efficacy trials and labeling at approval to evaluate if FDA recommendations were implemented. Of these 40 recommendations for efficacy trials, 35 (88%) were considered supportive of individualized dosing. Eighteen of these 40 recommendations (45%) were incorporated into efficacy trials and 11 (28%) were incorporated into labeling. This research suggests that early FDA‐sponsor interactions can support the study of doses in efficacy trials that may lead to individualized dosing strategies in labeling.

Wang, Lingshan↗
DOE OSTI2021

Tunable Photocatalytic Production of Syngas Using Co@C 3 N 4 and Black Phosphorus

Photocatalytic syngas production is an attractive option to efficiently generate a feedstock for the Fischer-Tropsch processes that can produce liquid fuels and other chemicals. Here, one-pot photocatalytic production of syngas (H 2 +CO) with specific and controllable ratios of H 2 /CO has proven to be a significant challenge to date. In this work, single Co 2+ sites loaded onto carbon nitride (Co@C 3 N 4 ) is combined with black phosphorus (BP) to form a hybrid material, which is capable of simultaneous photocatalytic evolution of H 2 and CO. H 2 /CO syngas ratios can be controlled in the range from 0.30 to 5.16 by changing the % weight of BP in this system or by the addition of CoCl 2 in the reaction solution. Maximum total gas evolution of 70 μmol g –1 h –1 was achieved with 20 wt % BP (BP 20% /Co@C 3 N 4 ) at a H 2 /CO ratio of 2.

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

Genetic correlations between switchgrass performance in sward conditions and surrogate measures

Switchgrass (Panicum virgatum L.) breeders use spaced-seedling plots for evaluations of biomass yield, but prior studies are ambiguous about the relationship between performance in spaced plots and commercial seeded sward performance. This study used a split-plot incomplete block design to evaluate 52 half-sib switchgrass families across two years to determine the correlations among four different plot types (including seeded swards) and four individual plant traits. Plots (1.62 m 2 ) that contained 3, 6, and 18 plants had mean yields of 5.92, 8.04, and 11.06 Mg ha –1 , respectively, while seeded-sward plots had a mean of 5.37 Mg ha –1 . In a mixed-model analysis including family-, year-, and plot-type interactions with a spatial-spline correction, the largest proportion of family variance was accounted for by the main family effect (48%), while the plot type-by-family effect was only 17% of family variance. These results indicate that spaced-plant plots are reasonable surrogates for biomass performance in sward conditions. Yield reliability was 0.50 across all plot types with a mean of 0.46 for individual plot types. Surrogates for sward yield varied due to genetic background of the families. Yield of families derived from the Liberty cultivar (n = 32) had genetic correlations with winter survivorship scores (0.66). Diverse lowland ecotype families (n = 20) had genetic correlations with plant height and heading date. This study highlighted a major difference in performance among the plot types, specifically that seeded swards have depressed yield due to high plant density. This should encourage further research for the mechanism behind this difference in performance.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Emerging Strategies for Modifying Lignin Chemistry to Enhance Biological Lignin Valorization

Biological lignin valorization represents a promising approach contributing to sustainable and economic biorefineries. Here, the low level of valuable lignin–derived products remains a major challenge hindering the implementation of microbial lignin conversion. Lignin's properties play a significant role in determining the efficiency of lignin bioconversion. To date, despite significant progress in the development of biomass pretreatment, lignin fractionation, and fermentation over the last few decades, little efforts have gone into identifying the ideal lignin substrates for an efficient microbial metabolism. In this Minireview, emerging and state–of–the–art strategies for biomass pretreatment and lignin fractionation are summarized to elaborate their roles in modifying lignin structure for bioconversion. Fermentation strategies aimed at enhancing lignin depolymerization for microbial utilization are systematically reviewed as well. With an improved understanding of the ideal lignin structure elucidated by comprehensive metabolic pathways and/or big data analysis, modifying lignin chemistry could be more directional and effective. Ultimately, together with the progress of fermentation process optimization, biological lignin valorization will become more competitive in biorefineries.

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

Approximation of ice phenology of Maine lakes using Aqua MODIS surface temperature data

Studies of lake ice phenology have historically relied on limited in situ data. Relatively few observations exist for ice out and fewer still for ice in, both of which are necessary to determine the temporal extent of ice cover. Satellite data provide an opportunity to better document patterns of ice phenology across landscapes and relate them to the climatological drivers behind changing ice phenology. We developed a model, the Cumulative Sum Method (CSM), that uses daytime and nighttime surface temperature observations from the Moderate Resolution Imaging Spectroradiometer (MODIS) sensor on board the Earth-observing Aqua satellite to approximate ice in (the onset of ice cover) and ice out from training datasets of 13 and 58 Maine lakes, respectively, during the 2002/2003 through 2017/2018 ice seasons. Ice in was signaled by reaching a threshold of cumulative negative degrees following the first day of the season below 0°C. Ice out was signaled by reaching a threshold of cumulative positive degrees following the first day of the year above 0°C. The comparison of observed and remotely sensed ice-in dates showed relative agreement with a correlation coefficient of 0.71 and a mean absolute error (MAE) of 9.8 days. Ice-out approximations had a correlation coefficient of 0.67 and an MAE of 8.8 days. Lakes smaller in surface area and nearer the Atlantic coast had the greatest error in approximation. Application of the CSM to 20 additional lakes in Maine produced a comparable ice-out MAE of 8.9 days. Ice-out model performance was weaker for the warmest years; there was a larger MAE of 12.0 days when the model was applied to the years 2019–2023 for the original 58 lakes. The development of this model, which utilizes daily satellite data, demonstrates the promise of remote sensing for quantifying ice phenology over short, temporal scales, and wider geographic regions than can be observed in situ, and allows exploration of the influence of surface temperature patterns on the process and timing of ice in and ice out.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Enhanced prediction of Cs removal by CST from Hanford tank waste with K accountability

Abstract The treatment of Hanford tank waste is one of the most challenging environmental cleanup activities to date. To expedite the processing of liquid waste stored in underground tanks in Washington State it is necessary to remove the significant dose contributor, 137 Cs. Crystalline silicotitanate ion exchanger is currently used to remove 137 Cs from the aqueous phase of Hanford tank wastes in preparation for vitrification at the Waste Treatment and Immobilization Plant (WTP). Improving the understanding of potassium impacts on ion exchange behavior of Cs will help in the operation of a critical component of one of the most complex treatment processes in the world today. Optimization of this process can result in significant cost savings and less waste production. Toward this effort, a series of batch contact tests varied in potassium concentration were conducted to look at the impact of potassium concentration on Cs distribution. Experimental distribution ratios ( K d ) were compared to the distribution ratios predicted using the ZAM model. A significant underprediction of Cs capacity in the presence of potassium was seen with the existing model. A revision of the equilibrium constants was determined and provided a statistically better fit for determining the Cs K d values in tank waste matrices.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2022

Application of ultrathin TiO 2 layers in solar energy conversion devices

Abstract A vital pursuit in solar energy research is to achieve high efficiency and long‐term stability in energy conversion devices. Coating or sandwiching an ultrathin layer of TiO 2 onto active solar components has been demonstrated to be a remarkably effective and facile strategy to improve their stability. The TiO 2 film acts as a protection layer and enhances solar energy conversion efficiency by passivating surface recombination sites or facilitating electron transport. To date, numerous efforts have been devoted to applying ultrathin TiO 2 layers in various kinds of solar energy conversion devices. In this study, we review deposition techniques, characterization methods of the resulting ultrathin TiO 2 layer, as well as its applications in dye‐sensitized solar cells, organic–inorganic hybrid solar cells, and photoelectrochemical cells.

36 MATERIALS SCIENCE↗