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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.

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At least 199 records · Page 11
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Capture and Decomposition of the Nerve Agent Simulant, DMCP, Using the Zeolitic Imidazolate Framework (ZIF-8)

Understanding mechanisms of decontamination of chemical warfare agents (CWA) is an area of intense research aimed at developing new filtration materials to protect soldiers and civilians in case of state-sponsored or terrorist attack. In this study, we employed complementary structural, chemical, and dynamic probes and in situ data collection, to elucidate the complex chemistry, capture, and decomposition of the CWA simulant, dimethyl chlorophosphonate (DMCP). Our work reveals key details of the reactive adsorption of DMCP and demonstrates the versatility of zeolitic imidazolate framework (ZIF-8) as a plausible material for CWA capture and decomposition. Here, the in situ synchrotron-based powder X-ray diffraction (PXRD) and pair distribution function (PDF) studies, combined with Fourier transform infrared (FT-IR) spectroscopy, X-ray photoelectron spectroscopy (XPS), zinc K-edge X-ray absorption near edge structure (XANES), and Raman spectroscopies, showed that the unique structure, chemical state, and topology of ZIF-8 enable accessibility, adsorption, and hydrolysis of DMCP into the pores and revealed the importance of linker chemistry and Zn 2+ sites for nerve agent decomposition. DMCP decontamination and decomposition product(s) formation were observed by thermogravimetric analysis, FT-IR spectroscopy, and phosphorus (P) K-edge XANES studies. Differential PDF analysis indicated that the average structure of ZIF-8 (at the 30 Å scale) remains unchanged after DMCP dosing and provided information on the dynamics of interactions of DMCP with the ZIF-8 framework. Using in situ PXRD and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), we showed that nearly 90% regeneration of the ZIF-8 structure and complete liberation of DMCP and decomposition products occur upon heating.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Spin diffusion in the Phosphorus-31 NMR relaxation in a layered crystalline α-Sn(IV) phosphate contaminated by paramagnetic impurities

The study of a layered crystalline Sn(IV) phosphate by solid-state NMR has demonstrated that the 31 P T 1 relaxation of phosphate groups, dependent on spinning rate is completely controlled by the limited spin diffusion to paramagnetic ions found by EPR. The spin-diffusion constant, D(SD), was estimated as 2.04 10 –14 cm 2 s –1 . Finally, the conclusion was supported by the 31 P T 1 time measurements in zirconium phosphate 1–1, also showing paramagnetic ions and in diamagnetic compound (NH 4 ) 2 HPO 4 .

1H MAS NMR↗
DOE OSTI2022

Past fires and post-fire impacts reconstructed from a southwest Australian stalagmite

Speleothem records of past environmental change provide an important opportunity to explore fire frequency and intensity in the past, and the antecedent climatic conditions leading to fire events. Here, fire sensitive geochemical signals in a stalagmite from Yonderup Cave, a shallow cave in Western Australia, are compared to well-documented wildfire events that occurred in recent decades. The results are extended to identify wildfires during the growth interval of the speleothem (1760 CE–2005 CE). Principal component analysis of the stalagmite time-series revealed distinct peaks in a combination of phosphorus and metal (aluminium, zinc, copper and lead) concentrations in response to known fire events, which are interpreted to have come from ash. Varying responses in the geochemical signal in the pre- and post-European colonisation period are likely linked to changes in land management, fire frequency and fire intensities. Of note is what we infer to be a particularly intense fire event concluded to have occurred in 1897 ± 5 CE, which climate sensitive proxies (δ18O and bedrock-derived elements) indicate was preceded by a multi-decadal dry period that began in the late 1860s. The intensity of the deduced fire event is supported by a peak in P that is 6.3 times higher than elsewhere in the speleothem, accompanied by a peak in Zn. It was also inferred that changes to the surface-cave hydrology occurred as a result of this event, indicated by increased input of colloidal organic material onto the stalagmite that was interpreted to be caused by shallow karst bedrock fracturing from the heat-induced deformation that is observed after intense fires. These findings show the potential for speleothems to provide dated records of fire intensity and recurrence intervals. Further development could lead to a better understanding of the climate-fire relationship and the effects of land-management practices on wildfire frequency and intensity.

58 GEOSCIENCES↗
DOE OSTI2020

Nano-FET-enabled biosensors: Materials perspective and recent advances in North America

Field-effect transistor (FET) is a very promising platform for biosensor applications due to its magnificent properties, including label-free detection, high sensitivity, fast response, real-time measurement capability, low running power, and the feasibility to miniaturize to a portable device. 1D (e.g. carbon nanotubes, Si nanowires, conductive polymer nanowires, 1D metal oxides, and others) and 2D (e.g. graphene materials, transition metal dichalcogenides, black phosphorus, and 2D metal oxides) materials, with their unique structural and electronic properties that are unavailable in bulk materials, have helped improve the sensitivity of FET biosensors and enabled detection down to single molecule. In this article, we give insights into the rapidly evolving field of 1D and 2D materials-based FET biosensors, with an emphasis on structure and electronic properties, synthesis, and biofunctionalization approaches of these nanomaterials. In addition, the progress in the 1D/2D-FET biosensors in North America, in the last decade, is summarized in tables. Moreover, challenges and future perspectives of 1D/2D-FET biosensors are covered.

1D materials↗
DOE OSTI2022

Whole-Ecosystem Warming Increases Plant-Available Nitrogen and Phosphorus in an Ombrotrophic Bog

Warming is expected to increase the net release of carbon from peatland soils, contributing to future warming. This positive feedback may be moderated by the response of peatland vegetation to rising atmospheric [CO 2 ] or to increased soil nutrient availability. We asked whether a gradient of whole-ecosystem warming (from + 0 °C to + 9 °C) would increase plant-available nitrogen and phosphorus in an ombrotrophic bog in northern Minnesota, USA, and whether elevated [CO 2 ] would modify the nutrient response. We tracked changes in plant-available nutrients across space and through time and in comparison with other nutrient pools, and assessed whether nutrient warming responses were captured by a point version of the land-surface model, ELM-SPRUCE. We found that warming exponentially increased plant-available ammonium and phosphate, but that nutrient dynamics were unaffected by elevated [CO 2 ]. The warming response increased by an order of magnitude between the first and fourth year of the experimental manipulation, perhaps because of dramatic mortality of Sphagnum mosses in the surface peat of the warmest treatments. However, neither the magnitude nor the temporal dynamics of the responses were captured by ELM-SPRUCE. Here, relative increases in plant-available ammonium and phosphate with warming were similar, but the response varied across raised hummocks and depressed hollows and with peat depth. Plant-available nutrient dynamics were only loosely correlated with inorganic and organic porewater nutrients, likely representing different processes. Future predictions of peatland nutrient availability under climate change scenarios must account for dynamic changes in nutrient acquisition by plants and microbes, as well as microtopography and peat depth.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

High-performance light-driven heterogeneous CO 2 catalysis with near-unity selectivity on metal phosphides

Akin to single-site homogeneous catalysis, a long sought-after goal is to achieve reaction site precision in heterogeneous catalysis for chemical control over patterns of activity, selectivity and stability. Herein, we report on metal phosphides as a class of material capable of realizing these attributes and unlock their potential in solar-driven CO 2 hydrogenation. Selected as an archetype, Ni 12 P 5 affords a structure based upon highly dispersed nickel nanoclusters integrated into a phosphorus lattice that harvest light intensely across the entire solar spectral range. Motivated by its panchromatic absorption and unique linearly bonded nickel-carbonyl-dominated reaction route, Ni 12 P 5 is found to be a photothermal catalyst for the reverse water gas shift reaction, offering a CO production rate of 960 ± 12 mmol g cat –1 h –1 , near 100% selectivity and long-term stability. Successful extension of this idea to Co2P analogs implies that metal phosphide materials are poised as a universal platform for high-rate and highly selective photothermal CO 2 catalysis.

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

Ultra‐Narrow Phosphorene Nanoribbons Produced by Facile Electrochemical Process

Abstract Phosphorene nanoribbons (PNRs) have inspired strong research interests to explore their exciting properties that are associated with the unique two‐dimensional (2D) structure of phosphorene as well as the additional quantum confinement of the nanoribbon morphology, providing new materials strategy for electronic and optoelectronic applications. Despite several important properties of PNRs, the production of these structures with narrow widths is still a great challenge. Here, a facile and straightforward approach to synthesize PNRs via an electrochemical process that utilize the anisotropic Na + diffusion barrier in black phosphorus (BP) along the [001] zigzag direction against the [100] armchair direction, is reported. The produced PNRs display widths of good uniformity (10.3 ± 3.8 nm) observed by high‐resolution transmission electron microscopy, and the suppressed B 2g vibrational mode from Raman spectroscopy results. More interestingly, when used in field‐effect transistors, synthesized bundles exhibit the n‐type behavior, which is dramatically different from bulk BP flakes which are p‐type. This work provides insights into a new synthesis approach of PNRs with confined widths, paving the way toward the development of phosphorene and other highly anisotropic nanoribbon materials for high‐quality electronic applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

The diversity and evolution of microbial dissimilatory phosphite oxidation

Significance Geochemical models of the phosphorus (P) cycle uniquely ignore microbial redox transformations. Yet phosphite is a reduced P source that has been detected in several environments at concentrations that suggest a contemporary P redox cycle. Microbial dissimilatory phosphite oxidation (DPO) converts soluble phosphite into phosphate, and a false notion of rarity has limited our understanding of its diversity and environmental distribution. Here we demonstrate that DPO is an ancient energy metabolism hosted by taxonomically diverse, autotrophic bacteria that exist globally throughout anoxic environments. DPO microorganisms are therefore likely to have provided bioavailable phosphate and fixed carbon to anoxic ecosystems throughout Earth’s history and continue to do so in contemporary environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Exploring Phosphonium‐Based Anion Exchange Polymers for Moisture Swing Direct Air Capture of Carbon Dioxide

This study explores the performance and stability of ammonium and phosphonium-based polymeric ionic liquids (PILs) with methyl and butyl substituents in moisture-swing direct air capture of CO 2 . The polymers are synthesized with chloride counterions, followed by ion exchange to the bicarbonate ion, and tests for CO 2 capture capacity and stability under cyclic wet–dry conditions. The phosphonium polymer with methyl substituents [PVBT-MeP] demonstrates the highest CO 2 capture capacity at ≈510 µmol g⁻¹, attributed to minimal steric hindrance and stronger ion pairing with bicarbonate. However, oxidative degradation is detected by 31 P NMR spectroscopy after the moisture swing experiment, with the appearance of a phosphine oxide peak at 61.28 ppm, which indicates phosphorus oxidation as the primary degradation pathway. In contrast, the ammonium polymer with butyl substituents [PVBT-BuN] exhibits the highest stability, showing no degradation over five moisture swing cycles. Additional stability experiments in 0.5 m KHCO 3 solutions reveal no degradation for any PIL, suggesting that oxidative degradation is driven by dynamic acid-base reactions during the moisture swing cycles in the air. Furthermore, these findings reveal the potential of phosphonium-based PILs for moisture-swing direct air capture, achieving high capacity while highlighting the need for optimized stability through counterion and structural design.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Layered zinc hydroxide as an adsorbent for phosphate removal and recovery from wastewater

At present, phosphate removal and recovery from wastewater is gaining wide attention due to the dual issues of eutrophication, caused by the increased production of algae, and universal phosphorus scarcity. In this study, a layered zinc hydroxide (LZH) was synthesized by a simple precipitation method and characterized via various techniques. Experiments investigating the effect of contact time, pH, LZH dose, initial phosphate concentration, and co-existing ions on phosphate adsorption were conducted. LZH exhibited a high phosphate adsorption capacity (135.4 mg g -1 ) at a neutral pH. More than 50% of phosphate was removed within the first 60 s of contact time at an initial phosphate concentration of 5 mg L -1 . Phosphate removal using the as-prepared LZH adsorbent was also tested in real treated sewage effluent reducing the residual phosphate amount to levels inhibiting to the growth of algae. Furthermore, phosphate desorption from LZH was investigated using acetic acid and sodium hydroxide regenerants which showed to be very effective for phosphate recovery.

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

A photosensitive sustainable lignin nanoplatform for multimodal image-guided mitochondria-targeted photodynamic and photothermal therapy

Photoactivated nanocarriers exhibit significant potential for anticancer therapy, but complex design strategies, unsustainable substrates, and short wavelengths limit their practical application. Here, we designed a new lignin-derived photoactivated nanomaterial that exploits the sensitivity of the β-O-4 bond of lignin to singlet oxygen. This sustainable product was loaded with mitochondria-targeting chlorin e6 and black phosphorus quantum dots (BPQDs) to produce BPQDs@N-LgC NPs, which were used for mitochondria-targeted fluorescence/photoacoustic-guided photothermal and photodynamic therapy. When irradiated at 808 nm, the BPQDs in BPQDs@N-LgC NPs exhibited good photothermal conversion, which allowed photoacoustic imaging and inhibited tumor growth. When irradiated at 660 nm, the BPQDs@N-LgC NPs generated fluorescence and reactive oxygen species, which allowed photoluminescence imaging and further inhibited tumor growth. Cleavage of the β-O-4 bond of lignin by photo-triggered reactive oxygen species degraded the NPs and released the BPQDs, facilitating rapid excretion of the therapeutic nanomaterials. Our rationally designed BPQDs@N-LgC NPs exhibited good therapeutic efficacy, both in vitro and in vivo.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Doping Limits of Phosphorus, Arsenic, and Antimony in CdTe

Low p-type doping is a limiting factor to increase CdTe thin-film solar-cell efficiency toward the theoretical Shockley-Queisser limit of 33%. Previous calculations predict relatively high ionization energies for group-V acceptors (P, As, and Sb) and they are plagued by self-compensation, forming AX-centers, severely limiting hole concentration. However, recent experiments on CdTe single crystals indicate a much more favorable scenario, where P, As, and Sb behave as shallow acceptors. Using hybrid functional calculations, we solve this puzzle by showing that the ionization energies significantly decrease with the supercell size. When including the effects of spin-orbit coupling and extrapolating the results to the dilute limit, we find these impurities behave as hydrogenic-like shallow acceptors, and AX-centers are unstable and do not limit ptype doping. We address the differences between our results and previous theoretical predictions and show that our ionization energies predict hole concentrations that agree with recent temperature-dependent Hall measurements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Creation of an Fe 3 P Schreibersite Density Functional Tight Binding Model for Astrobiological Simulations

The mineral schreibersite, e.g., Fe 3 P, is commonly found in iron-rich meteorites and could have served as an abiotic phosphorus source for prebiotic chemistry. However, atomistic calculations of its degradation chemistry generally require quantum simulation approaches, which can be too computationally cumbersome to study sufficient time and length scales for this process. In this regard, we have created a computationally efficient semiempirical quantum density functional tight binding (DFTB) model for iron and phosphorus-containing materials by adopting an existing semiautomated workflow that represents many-body interactions by linear combinations of Chebyshev polynomials. Here, we have utilized a relatively small training set to optimize a DFTB model that is accurate for schreibersite physical and chemical properties, including its bulk properties, surface energies, and water absorption. We then show that our model shows strong transferability to several iron phosphide solids as well as multiple allotropes of iron metal. Our resulting DFTB parametrization will allow us to interrogate schreibersite aqueous decomposition at longer time and length scales than standard quantum approaches, providing for more detailed investigations of its role in prebiotic chemistry on early Earth.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Heterogeneous hydroformylation of alkenes by Rh-based catalysts

Heterogeneously catalyzed hydroformylation reactions avert the problems of separation in homogeneous reactions, reduce the discharge of phosphorus-containing wastes, and prevent the loss of precious metals. This review summarizes the developments of catalysts for heterogeneous hydroformylation in the last decade and proposes potential modification methods for future improvements. The hydroformylation properties of different reactants are compared in order to emphasize the fact that various olefins face unique challenges. The hydroformylation of ethylene requires the enhancement of catalytic activity and chemoselectivity, whereas that of propylene needs improvements in both chemoselectivity and regioselectivity. The hydroformylation of longer-chain olefins and styrene seeks further improvement in regioselectivity. The catalytic properties of activity, selectivity, and stability can be tuned through electronic effects (bimetallic effects, phosphine ligands, and single-atom catalysts), steric hindrance (encapsulation structures, diphosphine ligands, and local functional groups), and reaction condition optimization (temperature, pressure, and solvents). Furthermore, the understanding of these effects is critical in future catalyst design for heterogeneous hydroformylation reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Local Structure of Glassy Lithium Phosphorus Oxynitride Thin Films: A Combined Experimental and Ab Initio Approach

Lithium phosphorus oxynitride (LiPON) is an amorphous solid–state lithium ion conductor displaying exemplary cyclability against lithium metal anodes. There is no definitive explanation for this stability due to the limited understanding of the structure of LiPON. Herein, we provide a structural model of RF–sputtered LiPON. Information about the short–range structure results from 1D and 2D solid–state NMR experiments. These results are compared with first principles chemical shielding calculations of Li–P–O/N crystals and ab initio molecular dynamics–generated amorphous LiPON models to unequivocally identify the glassy structure as primarily isolated phosphate monomers with N incorporated in both apical and as bridging sites in phosphate dimers. Structural results suggest LiPON's stability is a result of its glassy character. In conclusion, free–standing LiPON films are produced that exhibit a high degree of flexibility, highlighting the unique mechanical properties of glassy materials.

36 MATERIALS SCIENCE↗
DOE OSTI2020

CO 2 -Assisted propane aromatization over phosphorus-modified Ga/ZSM-5 catalysts

Modification of HZSM-5 with phosphorus (P) and gallium (Ga) was found to enhance the activity of CO 2 -assisted oxidative dehydrogenation and aromatization (CO 2 -ODA) of propane to liquid aromatics. Flow reactor studies measuring the simultaneous CO 2 reduction and the CO 2 -ODA of propane were performed at 873 K at atmospheric pressure over unmodified HZSM-5 and P/Ga/ZSM-5 catalysts. At comparable propane conversion, HZSM-5 showed a high selectivity toward the undesired methane product (41.4%) with a relatively low selectivity toward aromatics (16.5%). In comparison, P/Ga/ZSM-5 demonstrated a significantly higher aromatics selectivity (42.3%) with a simultaneous reduction in methane selectivity (13.5%). Density functional theory (DFT) calculations identified the mechanisms for propane dehydrogenation and aromatization over P/Ga/ZSM-5 and the role of CO 2 . Finally cooperative with P, CO 2 addition avoided the formation of molecular H 2 and reduced the barriers for benzene formation, leading to an enhanced activity and selectivity to aromatics from CO 2 -ODA of propane over P/Ga/ZSM-5.

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

Recovery of Rare Earth Element from Acid Mine Drainage Using Organo-Phosphorus Extractants and Ionic Liquids

Acid mine drainage is a legacy environmental issue and one of the largest pollutants in many mining districts throughout the world. In prior work, the authors have developed a process for the recovery of critical materials, including the rare earth elements, from acid mine drainage using a preconcentration step followed by solvent extraction as a concentration and purification technology. As part of the downstream technology development efforts, we have synthesized a suite of ionic liquid extractants that facilitate greater separation factors leading to lower capital costs and reduced environmental impacts. This article provides a comparison of the conventional extractants D2EHPA, EHEHPA and C572 with their respective ionic liquids [c101][D2EHP,c101][EHEHP] and [c101][C572] for the recovery of rare earth elements from acid mine drainage. In the study, laboratory-scale, multi-contact solvent extraction tests were conducted at high and low extractant/dosages. The results show that the ionic liquids varied in performance, with [c101][D2EHP] and [c101][EHEHP] performing poorer than their conventional counterparts and [c101][c572] performing better. Recommendations for further study on [c101][c572] include stripping tests, continuous pilot testing, and techno-economic analysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗