Search NASA⌕ Search

SEARCH · Search NASA

Results for “Oxygen extraction”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Gas scintillation mitigation in gas Cherenkov detectors for inertial confinement fusion (invited)

Gas Cherenkov detectors provide a time resolved measurement of the fusion burn in inertial confinement fusion experiments. The fusion rate delivers critical benchmark figures, such as burn width and bang time. Recent detector improvements pushed temporal resolution to 10 ps to make burn width measurements on igniting targets possible. First high temporal resolution measurements using CO 2 gas fills had a background signal with a long decay length (tail), which was caused by gas scintillation. This gas scintillation limits the ability of the detector to resolve short burn width and high frequency features in the fusion rate measurements. A thorough investigation of the cause of the tail and mitigation options for gas scintillation is presented here. As a near-term resolution, neon gas is being used to extract fusion burn histories. Paths forward for the next generation of gas Cherenkov detectors are identified including the usage of oxygen as a Cherenkov medium.

47 OTHER INSTRUMENTATION↗
DOE OSTI2022

Nuclear spectroscopy with heavy ion nucleon knockout and (p,2p) reactions

Knockout reactions with heavy ion targets in inverse kinematics, as well as “quasifree” (p,2p) and (p,pn) reactions are useful tools for nuclear spectroscopy. We report calculations on ab initio many-body wave functions based on the no-core shell model to study the nucleon removal reactions in light nuclei, including beryllium, carbon, and oxygen isotopic chains, and explore the importance of using an ab initio method. Our study helps to clarify how the extraction of spectroscopic factors from the experiments depend on the details of the many-body wave functions being probed. We show that recent advances with the ab initio method can provide more insights on the spectroscopy information extracted from experiments.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2021

Multiscale Catalytic Fast Pyrolysis of Grindelia Reveals Opportunities for Generating Low Oxygen Content Bio-Oils from Drought Tolerant Biomass

Grindelia squarrosa (curlycup gumweed) biomass possesses unique biochemistry, cell wall composition, and leaf architecture tailored for prolific growth in arid and semiarid climates. Most notably, this plant has developed high levels of extractable resins that have high effective H/C eff ratios ((mol H - 2 x mol O)/mol C), which is hypothesized to lead to low coke formation during catalytic fast pyrolysis (CFP) over the ZSM-5 catalyst. In microscale experiments with high ZSM-5 loadings (biomass-to-catalyst mass ratio (B/C) ~ 0.1), in situ CFP generated high yields of aromatic hydrocarbons (30% carbon yield) while ex situ CFP favored aliphatic hydrocarbons (25% carbon yield). The difference between the two configurations was attributed to the constant catalyst temperature during ex situ CFP. Deactivation leading to partially deoxygenated vapor products occurred rapidly until B/C ≤ 0.5 by the adsorption of organic species blocking access to acid sites inside the micropores of the catalyst. This was followed by more gradual deactivation leading to primary vapor breakthrough, which we attribute to coke formation on acid sites on the external surface of ZSM-5 crystallites. Noncatalytic fast pyrolysis of Grindelia in a bench scale reactor produced oils with oxygen content (18 wt % on dry basis) and carbon yield (33%) comparable to those of CFP of woody biomass. The CFP of Grindelia further reduced the oxygen content to 7 wt % for in situ CFP and 4 wt % for ex situ CFP at B/C of 2-3. The good deoxygenation was attributed to a combination of a high H/C eff ratio and overall better quality of the pyrolysis vapors that were passed over the ZSM-5 catalyst. The high inorganic content of the Grindelia likely catalyzed pyrolysis to remove oxygenated coke precursors. This integrated CFP study demonstrated that Grindelia could be an important feedstock for generating stabilized noncatalytic and CFP oils for downstream processing into fuels and/or extraction of high-value chemicals. The preprocessing of this feedstock will be required to remove inorganics, which cause an irreversible deactivation of ZSM-5.

BIOMASS FUELS↗
DOE OSTI2022

Impact of Tree Age and Anatomical Fraction on Forest Residue Pyrolysis and Hydrotreating

Utilization of cost-advantaged biomass and waste resources to produce clean, domestic biofuels will be a key factor in decarbonizing transportation in the United States. This study investigates how the distribution of anatomical fractions (stem wood, bark, needles, branches) from pine forest residues of different ages impacts pyrolysis and hydrotreating processes, including product composition, carbon efficiency, economics, and overall sustainability. Commercially sourced 13- and 23-year-old loblolly pine residues were chosen to represent available resources; whole tree thinnings, and tops and branches from merchantable timber, respectively. Detailed characterization of the residue samples, product distributions, bio-oil, char, and gas characterization data are presented for 13 experiments, including the individual fractions, blends, and air-classified samples to reduce ash content. Pyrolysis mass balances averaged 97 +/- 3%. As expected, bio-oil yields were lower for the bark, needles, and blends with high proportions of these (53-56% dry basis), and highest for the debarked stem wood (67-71% dry basis). Lower yields were attributed to the high ash content of the needles, but also to the high lignin content in the bark (>50%), which is hypothesized to have led to increased char formation during pyrolysis. Higher-oil yield was generally correlated with total volatiles, hydrogen, oxygen, glucan, and mannan; somewhat correlated with xylan and acetyl content; and negatively correlated with total carbon, fixed carbon, nitrogen, sulfur, and extractives. Air classification of the residues was effective in reducing ash content (1.5% to 0.64%), extractives (~7% to 2%), and sulfur (0.04% to 0.02%), resulting in a small increase in yield, a significant increase in the GC-detectable proportion of oil (27% to 34%) and a net economic benefit. These experimental results were used to conduct technoeconomic and life cycle analyses, which are also summarized here.

biofuels↗
DOE OSTI2022

Enhanced Light Outcoupling from OLEDs Fabricated on Novel Low-Cost Patterned Plastic Substrates of Varying Periodicity

OLEDs continue to make strides in display applications, but their commercial utilization in solid-state lighting (SSL) is lagging. An ongoing challenge, in particular for manufacturing, is the need for enhanced efficiency and hence the necessity to increase in an inexpensive approach the extraction of the light generated inside the OLED into the forward (viewing) hemisphere. In conventional OLEDs fabricated on a transparent flat anode coated on glass, the external quantum efficiency (EQE) is only ~20%. About 50% of the light is lost to internal waveguiding in the high refractive index (RI) organic + ITO anode layers and to surface plasmon polaritons (SPPs) at the organic/metal cathode interface. Another ~30% of the light is externally waveguided in the substrate to its edges. While extraction of the externally waveguided light is commonly addressed by adding a microlens array (MLA) or a scattering layer at the substrate’s air-side, light outcoupling increases by only ~1.6-1.7x (vs up to 2.5x in improving from ~20% to ~50%). The use of a hemispherical lens or an index matching fluid (IMF) at the substrate/photodetector (PD) interface increases the outcoupling by at least 2x; these approaches however, are not viable industrially, and even a MLA is sometimes undesirable due to its non-planar, scattering structure. In multi-stack tandem OLEDs, where the metal cathode is far from the emitting zone(s), the impact of photons loss to SPPs decreases. Our project addressed the ~50% loss to the internally waveguided light and SPPs. We evaluated OLEDs fabricated on patterned or planarized plastic substrates manufactured in a cost-effective approach compatible with a roll-to-roll (R2R) process. The OLEDs were either (i) patterned to various degrees depending on the pitch a and height or depth h of the pattern features or (ii) planar, with a pattern buried under a flat high RI planarization layer. We demonstrated that the outcoupling from green patterned OLEDs reaches ~50% by mitigating plasmon–related loss and internal waveguiding, even without the addition of a MLA, a hemispherical lens, or IMF. Simulations conducted in parallel with the experimental effort demonstrated how diffraction by conformally corrugated OLEDs increases the outcoupling to >60%. Structures with varying pitch values were also simulated indicating that combining domains of varying pitch could increase outcoupling to 55-60%. Experimentally, we additionally assessed the role a and h in determining not only the OLED efficiencies, but also their structural properties, i.e., the uniformity and conformality throughout the OLED stack. As planar OLEDs are preferred over corrugated devices, we studied different patterns in plastic substrates that were planarized by a high RI formulation. Planar green OLEDs on such structures showed enhanced efficiencies with EQEs larger than 60% with the addition of an IMF (to extract the substrate mode) at the substrate/Si PD interface. White OLEDs showed EQEs of 45.5%. Plastic substrates are currently less attractive than glass substrates due to drawbacks such as permeability to water vapor and oxygen, and in some cases thermal instability. Plastic substrates however, are flexible and easy to handle unlike thin flexible glass, and once transparent thin barrier films are available, they will become more attractive; they are already of interest in medical applications. Importantly, as it is easy to generate various patterns in different plastic materials, they provide excellent means for assessing and optimizing enhancing extracting structures. Such structures can also be transferred to glass substrates with some process modifications. The technical effectiveness and economic feasibility of the project lie in the patterning of the extracting plastic substrates in an approach that is scalable to R2R manufacturing. R2R processes are of drastically lower-cost than batch or single-unit fabrication. The patterned plastic can be a part of an integrated substrate either plastic or glass, which includes also a MLA or a planar layer with embedded scattering particles, as well as a conductive metal mesh/electrode design. SSL is environmentally-friendly and as OLED SSL becomes more efficient it will reduce electricity consumption, and hence lighting cost, as well as produce less expensive attractive lighting fixtures. Our university-industry collaboration is hence of major benefit to the public as it demonstrates the feasibility of manufacturing optimized extracting substrates for highly efficient OLEDs for SSL in a future R2R process, which would drastically reduce the manufacturing cost and increase production in the USA. Moreover, newly developed methods by our team allow low-cost roll manufactured substrates to be transferred to flexible or rigid glass substrates, which solves the plastic substrate barrier issues, and when combined with device encapsulation will increase the OLEDs’ environmental stability.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2025

Advanced Brine Processing to Enable U.S. Lithium Independence (CRADA Report)

Current production of LiOH, which is needed to make Li-ion battery cathode active materials, utilizes a multistep process including solar evaporation, precipitation with Na 2 CO 3 and then conversion to LiOH using Ca(OH) 2 . This process requires a large amount of land area for solar evaporation, the right weather conditions, and chemicals for the conversion process that result in NaCl and CaCO 3 waste products. The production of Ca(OH) 2 is very energy intensive and evolves significant quantities of CO 2 . An alternative process flow utilizing direct lithium extraction techniques, followed by a chemical free conversion process can have benefits in reducing the needed land requirements and chemicals for traditional brine processing. There are many potential direct lithium extraction technologies that are currently being developed. The direct lithium extraction process from typical brine sources will produce a LiCl solution with some impurities including typically high concentrations of Na. This brine then needs to be converted to LiOH for use in battery cathode production. Ideally this conversion could occur without the use of additional chemicals. Electrochemistry can do this conversion either via electrolysis or bipolar membrane electrodialysis (BPED) to produce LiOH and HCl in solution. BPED utilized bipolar membranes to split water, which has a reduced potential as compared to splitting water at electrodes into hydrogen and oxygen gas. This reduced potential required results in a significant energy savings for BPED over electrolysis methods. This CRADA project aimed to develop such an integrated process using direct lithium extraction followed by BPED to produce a LiOH solution. That solution can then be crystallized into battery grade LiOH. In particular, Albemarle utilized a direct lithium extraction process to produce a concentrated LiCl solution that could be used for the BPED process. The BPED process was first tested using various LiCl solutions with impurity ions added at bench scale to understand the effects of impurities and determine processing parameters. Then testing was performed using the direct lithium extracted brine at the bench scale before scaling the process up. After the process was scaled up a long duration test was carried out to estimate the lifetime of the membranes, which is key to the economics of the BPED process.

25 ENERGY STORAGE↗
DOE OSTI2025

Sustainable upcycling of polyethylene waste to compatibilizers and valuable chemicals

Controllable functionalization of polyethylene (PE) waste could generate new polymeric materials that are generally difficult to manufacture sustainably while also addressing the growing plastics waste problem. However, these modifications remain challenging due to the inherent stability of the PE backbone. Non-thermal atmospheric plasma enables molecular activation under mild conditions while utilizing renewable energy but is primarily employed for surface modification, as plasmas do not penetrate the bulk of materials. Herein, controllable bulk oxidative functionalization of PE wax (PEW) and low-density PE (LDPE) of varying molecular weights was achieved, with up to 6 mol% oxygen incorporation, by manipulating melt viscosity. This functionalization was accomplished either through temperature adjustment or by introducing a melt viscosity modifier, removable via simple extraction methods, to reduce LDPE viscosity, enhance diffusion and chain mobility, and enable bulk oxidation. The oxidized LDPE induces compatibilization in blends of poly(lactic acid) (PLA) and LDPE with improved interfacial adhesion and mechanical properties, such as a 70% increase in elongation-at-break values vs. the control. These findings pave the way for catalyst-free upcycling of direct plastics waste and plastics waste-derived products, enabling the creation of high-value products across various markets.

Plastic upcycling↗
DOE OSTI2023

Comparing the response of the indigenous microbial community to crude oil amendment in oxic versus hypoxic conditions

The Caspian Sea is the world’s largest landlocked saline lake which lies between Europe and Asia. This region is particularly known for its large-scale oil reserves, pipelines, and drilling activities, which have contributed to the environmental decline of this lake. In addition to pollution from the petroleum industry, drainage from various river basins brings an influx of residential, industrial, and agricultural effluents that induce eutrophication and hypoxic conditions in deeper, colder waters, creating an oxygen gradient. The temperature and oxygen stratification in this environment has presented a unique opportunity to investigate the potential of the biodegradative processes carried out by the indigenous microbial community. We believe these indigenous microbes possess different metabolic capabilities to degrade oil as they adapted to declining oxygen concentrations and temperatures with increasing depths over a prolonged period. Hence, community structure and composition will vary with depth. Microcosms were set up to observe the indigenous microbial reaction after a 60 ppm native crude oil amendment over 115 days. Surface water microcosms were incubated at 28ºC and aerated while deep water microcosms were incubated at 8ºC under anaerobic conditions. These two environmental conditions represent the temperature and oxygen extremes along the gradient and were selected as we try to simulate the indigenous community’s response to this oil contamination. DNA was extracted and amplified from these microcosms and sequenced. Bioinformatic analysis was performed to track changes in the abundance of taxa present and biodiversity over different time points to show the progression of community structure. All microcosms showed the presence of hydrocarbon-degrading phyla, whose presence is consistent with other reports from oil-enriched environments. However, distinct communities were observed in oxic versus hypoxic microcosms. Orders of Bacteria related to sulfate and nitrogen cycling were found in hypoxic microcosms, indicating a possible mechanism for the anaerobic biodegradation of crude oil. GC-MS analysis of initial and final microcosms also provided evidence of degradation of hydrocarbon fractions in both warm, oxic and cold, hypoxic conditions.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Selectively extracting lithium from single and mixed cathode materials

With the burgeoning reliance on lithium-ion batteries for sustainable energy solutions and electric transportation, the environmental and resource management associated with battery disposal are increasingly critical. Addressing these challenges necessitates innovative recycling techniques that recover valuable battery components, particularly lithium. This research introduces a universal, eco-friendly approach tailored for the efficient selective extraction of lithium from both single and mixed cathode materials, achieving impressive selective leaching efficiencies of lithium (99.51 % for LFP, 90 % for NMC, and 97.24 % for mixed cathode). Surprisingly, leaching efficiency of lithium from NMC can be significantly improved by introducing LFP since LFP can remove the dense transition-metal salts on the surface of NMC. The extracted lithium is recovered as lithium carbonate with battery-grade purity. This study also highlights the reuse of formic acid and the adoption of oxygen as an oxidizing agent to prevent wastewater production. Therefore, this method provides a robust foundation for sustainable lithium battery recycling.

economically and environmentally feasible↗
DOE OSTI2022

Zero carbon solid-state rechargeable redox fuel for long duration and seasonal storage

Here, this work presents a unique thermochemical process for charging magnesium-manganese-oxide-based solid-state rechargeable redox fuel. High-temperature heating of the processing furnace can be driven by either renewable electricity or concentrated solar power. The simple recyclable fuel charging concept is based on a tubular falling bed reactor with countercurrent oxygen-depleted gas flow for complete heat recuperation. The main focus of this work is achieving solid flowability at high temperatures (1,450°C) and extracting chemically charged solid at ambient temperature with minimal energy loss. The operation strategies described in this work have enabled consistent magnesium-manganese-oxide particle flow up to 1,450°C. The measured extent of the thermal reduction reaction after cooling the particles is more than 90% of the fully reduced state at equilibrium. The thermal-to-chemical efficiency and overall system efficiency are 96% and 35% respectively, which are the highest reported for thermochemical fuels to date.

25 ENERGY STORAGE↗
DOE OSTI2021

ExoMars Mars Organic Molecule Analyzer (MOMA) Laser Desorption/Ionization Mass Spectrometry (LDI-MS) Analysis of Phototrophic Communities from a Silica-Depositing Hot Spring in Yellowstone National Park, USA

The Mars Organic Molecule Analyzer (MOMA) is a key scientific instrument on the ExoMars Rover mission. MOMA is designed to detect and characterize organic compounds, over a wide range of volatility and molecular weight, in samples obtained from up to two meters below the martian surface. Thorough analog sample studies are required to best prepare to interpret MOMA data collected on Mars. We present here the MOMA characterization of Mars analog samples collected from an alkaline silica depositing hot spring in Yellowstone National Park, WY, USA. These samples contain microbial streamer communities composed primarily of oxygenic and anoxygenic phototrophs. Additionally, in a study focused on detection of key classes of nonvolatile organics, samples of microbial streamers and their total lipid extract (TLE) have been measured on a MOMA Engineering Test Unit (ETU) instrument using its laser desorption/ionization mass spectrometry (LDI-MS) mode. MOMA LDI-MS detected a variety of lipids and pigments in the TLE sample. Species such as chlorophyll a were also detected from the streamer sample with the help of mass isolation. The results add to the LDI-MS sample characterization database, as well as demonstrate the benefit of using mass isolation on the MOMA instrument to reveal the presence of complex organics, and potential biomarkers, preserved in a natural sample, providing guidance to the in situ analysis of surface samples during Mars operations.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2026

Engineering Na‐Rich P2‐Type Layered Oxides Through Li/Ti Dual Doping for Oxygen Redox Activation and Superior Structural Stability

Sodium layered oxides Na x MO 2 (x ≤ 1 and M = transition metal ions) have gained significant interest as sodium-ion battery (NIB) cathodes owing to their high operating voltages and potential for higher energy density compared with polyanion and Prussian blue–type cathodes. However, their practical applications are often hindered by the irreversible structural transitions leading to capacity fading during cycling. The nature and substitution of transition metal ions define the material properties and electrochemical performance. In this study, through comprehensive electrochemical characterization combined with multi-scale structural and spectroscopical analyses, we demonstrate the synergistic impacts of Lithium and Titanium doping, which not only increases overall capacity by boosting cation and anion cooperative redox contributions but also improves the rate capability and cycling stability. Specifically, Li + doping enhances the available sodium inventory for extraction, while Ti 4+ disrupts Na + /vacancy ordering at lower voltages (< 4 V) and mitigates the detrimental P2→OP4/O2 phase transition during cycling. The combined effect of Lithium and Titanium doping promotes more charge localization on Oxygen, which activates reversible lattice oxygen redox reactions at elevated voltages, contributing additional capacity beyond conventional cationic redox. This work provides crucial insights into the design of high-performance, high-capacity P2-type layered cathode materials for sodium-ion batteries.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Numerical investigations to identify environmental factors for field-scale reactive transport of pathogens at riverbank filtration sites

While induced bank filtration is a proven method for facilitating sustainable drinking water production, it is at risk from surface water contaminations (e.g., pathogens). Induced bank filtration and pathogen transport in groundwater have been studied extensively. However, long-term studies that consider real-world conditions are missing. These conditions include seasonal changes to environmental conditions and waterworks operations. Therefore, to analyze the effect of seasonal changes on the transport of human pathogenic viruses and their indicators in induced bank filtration, concentrations of adenoviruses and pathogen indicators were monitored over 16 months at an active bank filtration plant at the Rhine River, in Düsseldorf (Germany). Based on this data, a 2D groundwater model was created in PFLOTRAN that simulated flow, heat transport, conservative transport of chloride and the resulting electrical conductivity, reactive transport of oxygen and nitrate, and colloid-based transport of coliforms, somatic coliphages, and adenoviruses. The results show that reduced travel time was the key factor determining periods with a low removal of coliforms and somatic coliphages in the aquifer. Travel time was controlled by river level variations during rainy seasons, and the waterworks extraction rates during dry seasons. Further, for adenovirus transport, travel distance in the subsurface appeared to be the key factor, while travel time had no significant impact. Coliform removal increased when the colmation layer permeability decreased, while coliphage and adenovirus removal was unaffected by the colmation layer permeability. Seasonal changes in temperature and oxygen content did not significantly impact the removal of coliphages and adenoviruses in groundwater. Denitrifying conditions correlated with a lowered coliform removal, but the modelling could not establish a connection between denitrifying conditions and coliform removal. Our study showed that removal of pathogens and pathogen indicators at induced bank filtration plants varies greatly in time and space (e.g., for coliforms from 1 to 4 log-levels at 20m travel distance), and that adenovirus transport differs considerably from transport of coliforms and somatic coliphages.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Biomanufacturing and bioprocessing of lunar regolith

Microbial biomanufacturing is important to accelerate lunar construction because it can leverage lunar material and waste streams as feedstocks to create a circular production system. In-space bio-mining and biomanufacturing using moon and asteroidal source material will enable the creation of infrastructure, produce industrial fuels and lubricants, and enable recovery of actinides and rare-earth elements (REEs) present in trace concentrations. Moreover, biomanufacturing in closed-loop systems (recycling and reuse of resources toward the establishment of a circular economy) will enable long-term lunar activities by recycling waste (CO 2 , gray water) and producing oxygen and biomaterials. Our response focuses on the use of lunar regolith and waste streams as feedstocks for protein and microbial-enabled biomining and bioprocessing to extract actinides and REEs, and to create biocomposites for lunar infrastructure. We envision an enclosed process that initiates with (1a) extracting actinides and REEs from lunar regolith using immobilized proteins, followed by (1b) creating biocomposites from the post-extracted lunar regolith for infrastructure, and (1c) cultivating diatoms and other microalgae on waste streams to harvest silica shells for incorporating into biocomposites and to generate O 2 for human respiration and/or producing refinable feedstocks. LLNL has significant expertise in all three processes and provides facilities, personnel, and expertise at the intersection of metal (lanthanide, actinide, transition) separations, purifications, biohydrometallurgy, radiobiochemistry, synthetic and systems biology, and materials science and engineering. Importantly, all three processes are relatively well-studied for Earth-based workflows and can be derisked for demonstration on the lunar surface by 2029.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Ca2+ Effects on Fe(II) Interactions with Mn-Binding Sites in Mn-Depleted Oxygen-Evolving Complexes of Photosystem II and on Fe Replacement of Mn in Mn-Containing, Ca-Depleted Complexes

Fe(II) cations bind with high efficiency and specificity at the high-affinity (HA), Mn-binding site (termed the “blocking effect” since Fe blocks further electron donation to the site) of the oxygen-evolving complex (OEC) in Mn-depleted, photosystem II (PSII) membrane fragments (Semin et al. in Biochemistry 41:5854, 2002). Furthermore, Fe(II) cations can substitute for 1 or 2Mn cations (pH dependent) in Ca-depleted PSII membranes (Semin et al. in Journal of Bioenergetics and Biomembranes 48:227, 2016; Semin et al. in Journal of Photochemistry and Photobiology B 178:192, 2018). In the current study, we examined the effect of Ca2+ cations on the interaction of Fe(II) ions with Mn-depleted [PSII(-Mn)] and Ca-depleted [PSII(-Ca)] photosystem II membranes. We found that Ca2+ cations (about 50 mM) inhibit the light-dependent oxidation of Fe(II) (5 µM) by about 25% in PSII(-Mn) membranes, whereas inhibition of the blocking process is greater at about 40%. Blocking of the HA site by Fe cations also decreases the rate of charge recombination between QA- and YZ•+ from t1/2?=?30 ms to 46 ms. However, Ca2+ does not affect the rate during the blocking process. An Fe(II) cation (20 µM) replaces 1Mn cation in the Mn4CaO5 catalytic cluster of PSII(-Ca) membranes at pH 5.7 but 2 Mn cations at pH 6.5. In the presence of Ca2+ (10 mM) during the substitution process, Fe(II) is not able to extract Mn at pH 5.7 and extracts only 1Mn at pH 6.5 (instead of two without Ca2+). Measurements of fluorescence induction kinetics support these observations. Inhibition of Mn substitution with Fe(II) cations in the OEC only occurs with Ca2+ and Sr2+ cations, which are also able to restore oxygen evolution in PSII(-Ca) samples. Nonactive cations like La3+, Ni2+, Cd2+, and Mg2+ have no influence on the replacement of Mn with Fe. These results show that the location and/or ligand composition of one Mn cation in the Mn4CaO5 cluster is strongly affected by calcium depletion or rebinding and that bound calcium affects the redox potential of the extractable Mn4 cation in the OEC, making it resistant to reduction.

calcium↗
DOE OSTI2020

Separation of High Purity Oxygenated Aromatics from Catalytic Fast Pyrolysis Organic Streams

Thermochemical conversion of lignocellulosic biomass offers an attractive route to produce fuels and chemicals. Specifically, catalytic fast pyrolysis (CFP) oils have been shown to contain a high concentration of oxygenated aromatics, which can be isolated as value-added co-products. Purification of oxygenated aromatics can be a viable pathway to more economically competitive biorefineries, yet the isolation of highly pure coproduct streams remains technically challenging due to the high chemical heterogeneity of thermochemical process steams. Here, we demonstrate an industrially scalable process for isolating phenol, a widely used precursor to plastics, from CFP oil. Importantly, we leverage standard industrial processes, such as distillation, liquid-liquid extraction, and crystallization, to achieve phenol with 97% purity. In addition, the primary distillation of the CFP oil yielded several other fractions that contain chemicals with the potential to be isolated (e.g. cyclic ketones, cresols, and guaiacols). This work provides a technically feasible path to high purity oxygenated aromatics that has the potential to offset fuel production costs in a biorefinery.

09 BIOMASS FUELS↗
DOE OSTI2024

Inkjet-printed SnO x as an effective electron transport layer for planar perovskite solar cells and the effect of Cu doping

Inkjet printing is a more sustainable and scalable fabrication method than spin coating for producing perovskite solar cells (PSCs). Although spin-coated SnO 2 has been intensively studied as an effective electron transport layer (ETL) for PSCs, inkjet-printed SnO 2 ETLs have not been widely reported. Here, we fabricated inkjet-printed, solution-processed SnO x ETLs for planar PSCs. A champion efficiency of 17.55% was achieved for the cell using a low-temperature processed SnO x ETL. The low-temperature SnO x exhibited an amorphous structure and outperformed high-temperature crystalline SnO 2 . The improved performance was attributed to enhanced charge extraction and transport and suppressed charge recombination at ETL/perovskite interfaces, which originated from enhanced electrical and optical properties of SnO x , improved perovskite film quality, and well-matched energy level alignment between the SnO x ETL and the perovskite layer. Furthermore, SnO x was doped with Cu. Cu doping increased surface oxygen defects and upshifted energy levels of SnO x , leading to reduced device performance. A tunable hysteresis was observed for PSCs with Cu-doped SnO x ETLs, decreasing at first and turning into inverted hysteresis afterwards with increasing Cu doping level. This tunable hysteresis was related to the interplay between charge/ion accumulation and recombination at ETL/perovskite interfaces in the case of electron extraction barriers.

14 SOLAR ENERGY↗