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NASA NTRS2003

Improved Process for Fabricating Carbon Nanotube Probes

An improved process has been developed for the efficient fabrication of carbon nanotube probes for use in atomic-force microscopes (AFMs) and nanomanipulators. Relative to prior nanotube tip production processes, this process offers advantages in alignment of the nanotube on the cantilever and stability of the nanotube's attachment. A procedure has also been developed at Ames that effectively sharpens the multiwalled nanotube, which improves the resolution of the multiwalled nanotube probes and, combined with the greater stability of multiwalled nanotube probes, increases the effective resolution of these probes, making them comparable in resolution to single-walled carbon nanotube probes. The robust attachment derived from this improved fabrication method and the natural strength and resiliency of the nanotube itself produces an AFM probe with an extremely long imaging lifetime. In a longevity test, a nanotube tip imaged a silicon nitride surface for 15 hours without measurable loss of resolution. In contrast, the resolution of conventional silicon probes noticeably begins to degrade within minutes. These carbon nanotube probes have many possible applications in the semiconductor industry, particularly as devices are approaching the nanometer scale and new atomic layer deposition techniques necessitate a higher resolution characterization technique. Previously at Ames, the use of nanotube probes has been demonstrated for imaging photoresist patterns with high aspect ratio. In addition, these tips have been used to analyze Mars simulant dust grains, extremophile protein crystals, and DNA structure.

Stevens, R.↗

DOE OSTI2025

Vanadium-enhanced Na 2 FePO 4 F cathodes for high-performance sodium-ion batteries

Sodium fluorophosphate Na 2 FePO 4 F holds great potential for sodium-ion batteries due to its high theoretical capacity, excellent structural stability, abundant resources, and affordability. However, its poor electronic and ionic conductivities limit its practical applications. Therefore, ion doping and carbon coating have been employed as synergistic strategies in this study to overcome these limitations. A one-step, energy-efficient solid-state method using sucrose as a carbon coating source was used to synthesize Na 2 FePO 4 F/C (NFPF/C) and its doped variant, Na 2 Fe 0.85 V 0.1 PO 4 F/C (NFVPF/C). 23 Na-MAS-NMR spectra confirm the existence of two distinct sites for sodium (Na1/Na2). The ex-situ 23 Na-MAS-NMR performed at different states-of-charge reveals the activity of only one sodium. The scanning electron microscopy findings reveal a reduction in the particle size with V-introduction, enhancing the energetic performances. NFVPF/C delivers higher specific capacity of 122 mAh g −1 compared to 116 mAh g −1 for NFPF/C at 0.1C. It also demonstrates improved cycling stability, retaining 81 % of its initial capacity after 120 cycles, in contrast to 46 % for the pristine material. The doped phase outperforms the pristine at higher current rates, delivering specific capacities of 81 and 55 mAh g −1 at 2C and 3C, respectively, compared to 35 and 17 mAh g −1 for NFPF/C.

25 ENERGY STORAGE↗

DOE OSTI2020

P-model v1.0: an optimality-based light use efficiency model for simulating ecosystem gross primary production

Terrestrial photosynthesis is the basis for vegetation growth and drives the land carbon cycle. Accurately simulating gross primary production (GPP, ecosystem-level apparent photosynthesis) is key for satellite monitoring and Earth system model predictions under climate change. While robust models exist for describing leaf-level photosynthesis, predictions diverge due to uncertain photosynthetic traits and parameters which vary on multiple spatial and temporal scales. Here, we describe and evaluate a GPP (photosynthesis per unit ground area) model, the P-model, that combines the Farquhar–von Caemmerer–Berry model for C 3 photosynthesis with an optimality principle for the carbon assimilation–transpiration trade-off, and predicts a multi-day average light use efficiency (LUE) for any climate and C 3 vegetation type. The model builds on the theory developed in Prentice et al. (2014) and Wang et al. (2017a) and is extended to include low temperature effects on the intrinsic quantum yield and an empirical soil moisture stress factor. The model is forced with site-level data of the fraction of absorbed photosynthetically active radiation (fAPAR) and meteorological data and is evaluated against GPP estimates from a globally distributed network of ecosystem flux measurements. Although the P-model requires relatively few inputs, the R 2 for predicted versus observed GPP based on the full model setup is 0.75 (8 d mean, 126 sites) – similar to comparable satellite-data-driven GPP models but without predefined vegetation-type-specific parameters. The R 2 is reduced to 0.70 when not accounting for the reduction in quantum yield at low temperatures and effects of low soil moisture on LUE. The R 2 for the P-model-predicted LUE is 0.32 (means by site) and 0.48 (means by vegetation type). Applying this model for global-scale simulations yields a total global GPP of 106–122 Pg C yr –1 (mean of 2001–2011), depending on the fAPAR forcing data. The P-model provides a simple but powerful method for predicting – rather than prescribing – light use efficiency and simulating terrestrial photosynthesis across a wide range of conditions. The model is available as an R package (rpmodel).

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS1990

Gas Sensor

High Technology Sensors, Inc.'s Model SS-250 carbon dioxide detector uses a patented semiconductor optical source that efficiently creates infrared radiation, which is focused through an airway on a detector. Carbon dioxide passing through the airway absorbs the radiation causing the detector to generate a signal. The small size and low power requirements of the SS-250 make it attractive for incorporation in a variety of medical instruments.

Source record↗

DOE OSTI2020

Co-solvents with high coulombic efficiency in propylene carbonate based electrolytes

A homologous series of cyclic carbonate or propylene carbonate (PC) analog solvents with increasing length of linear alkyl substitutes were synthesized and used as co-solvents with PC for graphite based lithium ion half cells. A graphite anode reaches a capacity around 310 mAh/g in PC and its analog co-solvents with 99.95% Coulombic efficiency. Cyclic carbonate co-solvents with longer alkyl chains are able to prevent exfoliation of graphite when used as co-solvents with PC. The cyclic carbonate co-solvents of PC compete for solvation of Li ion with PC solvent, delaying PC co-intercalation. Reduction products of PC on graphite surfaces via single-electron path form a stable Solid Electrolyte Interphase (SEI), which allows the reversible cycling of graphite.

25 ENERGY STORAGE↗

DOE OSTI2025

Synthesis of aerosol-cloud interactions over the southeast Atlantic throughout the seasonal cycle (Final Technical Report)

An analysis of the aerosol compositional, physical and optical datasets towards understanding why the single‐scattering‐albedo of smoke is so much lower over the southeast Atlantic than elsewhere, in particular the northern hemisphere. This includes data from the complementary NASA ORACLES aircraft campaign, which sampled closer to the African coast. The first analysis resulting from this prong of research was published earlier this year (Dobracki et al., 2023, ACP) and focused more on the free-tropospheric biomass burning aerosol (BBA). We primarily attributed the low SSA to a high number/mass fraction of black carbon, ranging from 15 to 40% of the total aerosol. We are further able to use other literature, the modified combustion efficiency, and the black carbon and carbon monoxide values to highlight a common source in dry, flame-efficient burning conditions of grasses. Condensation and coagulation of smaller aerosol particles onto the larger black carbon aerosols can also increased the SSA as the aerosol ages from 4 to 5 days. A comparison to data gathered over Ascension Island during the UK CLARIFY aircraft campaign indicates an organic aerosol loss relative to black carbon of about 50%. This is high compared to findings from other campaigns.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2019

Global vegetation biomass production efficiency constrained by models and observations

Typically, plants use only a fraction of their photosynthetically derived carbon for biomass production (BP). The biomass production efficiency (BPE), defined as the ratio of BP to photosynthesis, and its variation across and within vegetation types is poorly understood, which hinders our capacity to accurately estimate carbon turnover times and carbon sinks. In this work, we introduce a new global estimation of BPE obtained by combining field measurements from 113 sites with 14 carbon cycle models. Our best estimate of global BPE is 0.41 ± 0.05, excluding cropland. The largest BPE is found in boreal forests (0.48 ± 0.06) and the lowest in tropical forests (0.40 ± 0.04). Carbon cycle models overestimate BPE, although models with carbon–nitrogen interactions tend to be more realistic. Using observation-based estimates of global photosynthesis, we quantify the global BP of non-cropland ecosystems of 41 ± 6 Pg C/year. This flux is less than net primary production as it does not contain carbon allocated to symbionts, used for exudates or volatile carbon compound emissions to the atmosphere. Our study reveals a positive bias of 24 ± 11% in the model-estimated BP (10 of 14 models). When correcting models for this bias while leaving modeled carbon turnover times unchanged, we found that the global ecosystem carbon storage change during the last century is decreased by 67% (or 58 Pg C).

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2021

Case Study: Hybrid Carbon Conversion Using Low-Carbon Energy Sources in Coal-Producing States

The demand for more carbon efficient power sources and a decrease in natural gas prices has decreased the desire for coal power. This decrease in demand has led to massive job losses in coal mining regions over the past decade. The purpose of this project is to develop a hybrid energy system utilizing both a coal power plant and advanced reactor, which is competitive with natural gas by improving on profitability and decreasing carbon emissions. This report details the problem with a summary of the impact on the coal industry and the availability of renewable energy sources in the Appalachian region. Because of the geography of the region, variable renewable energy sources are not available without significant size and siting restrictions. However, biomass in the form of wood waste is abundant and can be used as a carbon neutral energy source. Combining biomass and coal processing, in addition to thermal power plants, can increase system profits and efficiency by providing peaking power and conversion opportunities for secondary markets. The electric load is based on publicly available demand data from Appalachian Power, which services the western Virginia and southern West Virginia in the Appalachian region. The demand information is combined by service, normalized, and scaled to an average demand of 1000 kW, which will be the basis for sizing the hybrid energy system. A traditional screening curve analysis for a coal plant and advanced reactor shows that the least cost design varies significantly based on the assumed discount rate and capital recovery period. An optimization program to size the design in TEAL based on the load curve gives 10 optimal designs, all with a negative resulting net present value (NPV) and a coal plant capacity of less than 15%. Including profits from selling captured carbon at a flat rate results in a positive NPV; however, the coal capacity factor only increases to about 40%. There are limitations with this optimization as well since the price of CO2 is likely to decrease as more is sold to the conversion market. The suggested design will combine coal power, an advanced reactor, and coal and biomass coprocessing to produce a variety of products that can be sold to the conversion market while increasing system efficiency. The analysis of conversion pathways for coal and biomass reveals that multiple options will need to be included in the analysis to produce the optimal system design. Three systems will be optimized and compared to determine the best design based on the figures of merit of total NPV and cost of carbon avoided. The first system will include a coal power plant and an advanced reactor that will sell electricity to the grid to meet demand and sell captured carbon to the conversion market. The second system adds a high-temperature steam electrolysis plant, which will utilize electricity during times of low demand to produce hydrogen and sell it to the conversion market. The third system adds biomass and coal processing with options for hydrocarbon oils, syngas to be produced for the conversion market, and electricity generation to power components within the system or provide peaking power. This analysis will be based on a new approach that combines traditional screening curve methods with a dispatch algorithm that optimizes the system based on the opportunity cost of different production options. The resulting optimization algorithm should provide results with less processing time than HERON’s decision tree method. The results from this analysis will determine an optimal design and reinforce the benefits of coal power when used in a hybrid energy system. The initial results show that the addition of a secondary market for carbon sales could result in a positive NPV and increases the capacity factor of the coal plant as compared to a design with only sales to the electricity market. The addition of more markets and additional coal consumption from biomass coprocessing could increase NPV further, replace carbon in other markets through the sale of biomass-derived hydrocarbons, and demonstrate the value of coal power technology.

01 COAL, LIGNITE, AND PEAT↗

DOE OSTI2021

Precursor Processing Development for Low Cost, High Strength Carbon Fiber for Composite Overwrapped Pressure Vessel Applications

Carbon fiber (CF) is central to produce lightweight, high pressure, composite overwrapped pressure vessels (COPVs), which are used for on-board storage of hydrogen for fuel cell vehicles. In 2015, carbon fiber cost accounted for 62% of the cost of a hydrogen storage system, as COPVs were manufactured with T700S CF at $\$ $29.40/kg CF. The high cost of hydrogen storage, largely attributed to the carbon fiber cost, limits the application of fuel cells in vehicles. Therefore, our team endeavored to develop fiber processing to demonstrate carbon fiber tensile properties similar to T700S with a production cost potential of $\$ $12.60/kg or less. Here, the overarching goal of the project was the development of low cost, high strength carbon fiber for composite overwrapped pressure vessels. Within the project, our team investigated a new low-cost, high-volume, high quality polyacrylonitrile (PAN)-based precursor terpolymer for the production of carbon fiber precursors, methods for increasing water and energy use efficiency in wash-water/solvent separation, and ultimately developed a multifilament spinning and conversion process for the production of hollow carbon fibers from a segmented arc spinneret utilizing a solution spinning method.

08 HYDROGEN↗

DOE OSTI2023

Nexus of electrification and energy efficiency retrofit of commercial buildings at the district scale

Rapid electrification of buildings at the district scale is needed for cities to achieve climate change mitigation goals. However, most electrification studies focus on either the single building level or the city/region building stock level, and depend on the slow and uncertain process of requesting personally identifiable customer energy usage data from utilities. To answer a key question facing local policymakers: “Where can electrification proceed at scale without first upgrading the grid?” this study aims to quantify and inform building electrification impacts at the district scale using detailed building energy modeling and based on public records datasets. We explore how energy efficiency retrofits can help mitigate increased peak electric demand, and quantify impacts to energy use and carbon emissions. Building energy models of a baseline, and scenarios of simple electrification, energy retrofits, and electrification in combination with retrofits were created and simulated for 54 commercial buildings in two contiguous districts of San Francisco. A simple electrification scenario increased annual electricity consumption but reduced annual site energy usage by 15% to 17%, mainly due to replacing inefficient gas furnaces and boilers with more efficient heat pumps. Peak demand increased 7.4% for Fisherman's Wharf (e.g. within the capacity of the existing power grid), while the Design District showed a marginal decrease. Annual carbon emissions were reduced by 46% and 37%. Combining electrification with efficiency upgrades reduced peak demand by 26% and 40%, and annual carbon emissions by 63% and 64% for the two districts. Furthermore, these results indicate that impacts of electrification depend on the mix of building uses within a district, and coupling electrification with energy efficiency upgrades is an effective strategy to decarbonize buildings while maintaining or reducing the peak electric demand.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

DOE OSTI2020

High Vapor Pressure Deficit Decreases the Productivity and Water Use Efficiency of Rain‐Induced Pulses in Semiarid Ecosystems

Abstract Intermittent rain events drive dynamic pulses of carbon and water exchange in many arid and semiarid ecosystems. Although soil moisture is known to control these pulses, the effect of atmospheric dryness on pulses is not well documented. Here we hypothesized that vapor pressure deficit ( VPD ) modulates net ecosystem production ( NEP ) and ecosystem‐scale water use efficiency ( WUE ) during pulse events due to its effects on canopy stomatal conductance and evapotranspiration. We quantified relationships between VPD and carbon and water exchange during growing season rain events and tested their generality across four semiarid flux sites with varied vegetation in the southwest United States. Across grassland, shrubland, and savanna sites, we found that high VPD during pulses suppressed ecosystem photosynthesis and surface conductance to a greater degree than respiration or evapotranspiration, particularly when soil moisture was high. Thus, periods of high VPD were associated with a 13–64% reduction in NEP and an 11–25% decrease in WUE , relative to moderate VPD conditions. Sites dominated by shrubs with the C3 photosynthetic pathway were more sensitive to VPD than sites dominated by C4 grasses. We found that a 1 kPa increase in VPD reduced the average NEP of pulse events by 13–56%, which illustrates the potential for projected increases in atmospheric demand to reduce the net productivity of semiarid ecosystems.

Roby, Matthew C.↗

DOE OSTI2024

Leaf-level physiological strategies related to productivity and plasticity of Populus in the Southeastern United States

Introduction: Populus and its hybrids are attractive bioenergy crops and the southeastern United States has broad ability to supply bioenergy markets with woody biomass. Breeding and hybridization have led to superior eastern cottonwood (Populus deltoides W. Bartram ex Marshall) and hybrid poplars adapted to a wide variety of site types not suited for agricultural production. In order to maximize productivity and minimize inputs, genotypes need to efficiently use available site resources and tolerate environmental stresses. In addition, we need to determine plasticity of traits and their coordination across sites to select traits that will broadly characterize genotypes. Therefore, our study objectives were to determine (1) which leaf traits were correlated with growth, (2) if traits and genotypes exhibited significant plasticity across sites, and (3) how traits were coordinated within and across sites and Populus taxa. Methods: We measured trees at two sites in northeastern Mississippi, United States: one upland and one alluvial terrace site. Genotypes included eastern cottonwoods as well as F 1 crosses of eastern cottonwood and P. maximowiczii (Henry), P. nigra (L.) and P. trichocarpa (Torr. & Gray). Results: We found that sites differed in which leaf traits were correlated with productivity; with water use efficiency specifically being positively correlated with growth at an alluvial terrace site, but negatively correlated with growth at an upland site. Tree height growth, leaf isotope composition (δ 13 C and δ 15 N), as well as leaf mass per area (LMA) exhibited the least plasticity across sites, while physiological gas exchange parameters and leaf nitrogen concentration exhibited the highest plasticity. Broadly across taxa, leaf carbon isotope ratios were correlated with intrinsic water use efficiency, and stomatal conductance was positively correlated with photosynthetic nitrogen use efficiency across sites, while leaf nitrogen isotope ratios exhibited contrasting relationships with leaf nitrogen concentration. Discussion: Overall, these results allow us to refine selections of productive genotypes based on site conditions and site-specific relationships with physiological parameters to better match Populus taxa with sites and landowner objectives.

bioenergy feedstocks↗

DOE OSTI2021

n-Butanol production by Rhodopseudomonas palustris TIE-1

Anthropogenic carbon dioxide (CO 2 ) release in the atmosphere from fossil fuel combustion has inspired scientists to study CO 2 to biofuel conversion. Oxygenic phototrophs such as cyanobacteria have been used to produce biofuels using CO 2 . However, oxygen generation during oxygenic photosynthesis adversely affects biofuel production efficiency. To produce n-butanol (biofuel) from CO 2 , here we introduce an n-butanol biosynthesis pathway into an anoxygenic (non-oxygen evolving) photoautotroph, Rhodopseudomonas palustris TIE-1 (TIE-1). Using different carbon, nitrogen, and electron sources, we achieve n-butanol production in wild-type TIE-1 and mutants lacking electron-consuming (nitrogen-fixing) or acetyl-CoA-consuming (polyhydroxybutyrate and glycogen synthesis) pathways. The mutant lacking the nitrogen-fixing pathway produce the highest n-butanol. Coupled with novel hybrid bioelectrochemical platforms, this mutant produces n-butanol using CO 2 , solar panel-generated electricity, and light with high electrical energy conversion efficiency. Overall, this approach showcases TIE-1 as an attractive microbial chassis for carbon-neutral n-butanol bioproduction using sustainable, renewable, and abundant resources.

60 APPLIED LIFE SCIENCES↗

DOE OSTI2025

Techno-economic analysis of indirect carbonation processes for carbon sequestration using mining waste

A comprehensive assessment of process design, cost efficiency, critical mineral recovery, and CO 2 storage in mine tailings.

Gomes, Katherine Vaz [Department of Chemical and B↗

DOE OSTI2022

Choosing the Best Carbon Factor for the Job: Exploring Available Carbon Emissions Factors and the Impact of Factor Selection

Over 600 local governments in the United States, including nearly half of the largest 100 cities, have enacted climate action plans that include carbon reduction goals and greenhouse gas inventories (Markolf et al. 2020). The magnitude of these goals ranges from modest reduction targets to carbon neutrality. None will be met without significant contributions from the buildings sector. Understanding how energy efficiency and building electrification impact greenhouse gas emissions requires local, time-sensitive, and forward-looking carbon emissions factors for electricity use in buildings. There are a variety of emissions factors currently available from various sources, including average emissions factors and historical short-run marginal emissions factors. Long-run marginal emissions factors and future-year short-run marginal emissions factors are also now available from the National Renewable Energy Laboratory's (NREL's) Cambium data sets. In this paper, we describe the different carbon emissions factors available, including both conventional sources and newly available options. We discuss the types of analyses each emissions factor is best suited to support. Then, using residential energy efficiency and electrification load profiles, we demonstrate how different conclusions result from different choices of carbon emissions factors. For two grid regions, we explore takeaways of using current versus future-year emissions, short-run versus long-run, and levelized versus single-year values. We include a framework for selecting the best carbon emissions factor for the job.

carbon emissions factors↗

DOE OSTI2024

Choosing the Best Carbon Factor for the Job: Exploring Available Carbon Emissions Factors and the Impact of Factor Selection: Preprint

carbon emissions factors↗

DOE OSTI2022

Susceptibility of new soil organic carbon to mineralization during dry-wet cycling in soils from contrasting ends of a precipitation gradient

The persistence of soil organic carbon (SOC) is influenced by soil physicochemical properties, organic matter quality, and climatic conditions that govern its vulnerability to microbial activity. We compared the susceptibility of newly formed SOC to mineralization in two soils (Andosols) that developed under contrasting precipitation regimes. Soil from the high rainfall region (‘high rain ’) had higher SOC and lower iron concentrations than soils exposed to less rainfall (‘low rain ’). We amended soils with 13 C-labeled carbohydrates and measured the amount of substrate-derived SO 13 C mineralized when exposed to dry-wet cycling following months-long incubations. We hypothesized that susceptibility would differ due to iron content and mineralogy, initial SOC, substrate solubility (cellulose versus glucose amendment), and microbial substrate use efficiency (SUE). We found that SO 13 C was less susceptible to dry-wet cycling when more 13 C was assimilated into microbial biomass and co-localized with mineral surfaces than when co-localized with existing organo-mineral surfaces, according to microscale NanoSIMS imaging. Considerably less SO 13 C was susceptible to mineralization in the ferrihydrite-rich (low SOC) low rain soil than the leached (high SOC) high rain soil when C was added as either glucose (7.3-fold less C mineralized) or cellulose (15.2-fold less). Additionally, the SUE of glucose was comparable to cellulose in low rain soil where SO 13 C was less water soluble and coprecipitated with ferrihydrite, and used half as efficiently as cellulose in high rain soil. Our results show that the susceptibility of newly formed SOC to mineralization is modified by the effects of bioavailability on microbial metabolism and the availability of mineral surfaces for forming new organo-mineral complexes.

21 NanoSIMS↗

DOE OSTI2025

Carbonation of Alkaline Earth Metal Hydroxides: Structure across Nano- to Mesoscales

The conversion of gaseous CO 2 into a solid constitution through mineralization is an active area of carbon capture, and alkaline earth metal hydroxides (M(OH) 2 , M = Ca 2+ , Mg 2+ ) are frontrunners in this area. As model systems, nanolime samples are excellent templates for the study of this reaction. Here, we have examined these under ambient pressure conditions with controlled humidity and CO 2 . Utilizing a broad range of analytical methods, we first established the purity and structures of the selected materials. We then examined the structural changes due to carbonation, using infrared spectroscopy, X-ray scattering, and neutron scattering. The resulting structural changes are resolved from nanoscale to mesoscale and from early-stage to late-stage carbonation. Ca(OH) 2 and Mg(OH) 2 are found to behave quite differently. As expected from prior work, the carbonation of Ca(OH) 2 is kinetically favored. Further, our structure studies suggest this is due to a facile reaction at the fractal interface of the particles. From early- to late-stage carbonation, there is a consistent increase in the fractal roughness. This is in contrast to Mg(OH) 2 where the same surface evolves into a smooth conformal coating. For this material the major reacting component is at the mesoscale, suggesting globular particle growth or evolving macro-porosity. Because neutron scattering is sensitive to hydrogen content, we expected a significant change as M(OH) 2 evolves to MCO 3 . Such a change is found for Ca(OH) 2 but not for Mg(OH) 2 , providing evidence for the formation of hydrated carbonates for the later material. The formation of a conformal layer along with water-rich carbonate formation is an impediment to the use of Mg(OH) 2 for carbon capture. For energy-efficient carbon capture, it would be desirable to enhance carbonation rates for Mg(OH) 2 , and one possible route would be the use of anhydrous fluids.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗