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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 1,459 records · Page 81
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Development of Mixed-Salt Technology for CO 2 Capture from Coal Power Plants

SRI International (SRI), in collaboration with Stanford University, OLI Systems (OLI), Politecnico de Milano (PoliMi), and Aqueous Systems Aps (ASApS) performed a 45-month effort to develop a promising Mixed-Salt Process (MSP) for carbon dioxide capture. The MSP combines existing ammonia and potassium-carbonate technologies with improved absorption steps for rate enhancement and ammonia emission reduction and a novel selective regeneration process with a high-pressure CO 2 product to introduce a new and advanced transformational solvent-based technology. The striking advantages of the SRI MSP include: low heat of reaction, high loading of CO 2 , high-pressure regeneration of > 99% pure dry CO 2 , low sensitivity to impurities, low process cost, use of a non-degradable low-cost solvent with a very low carbon footprint for its production, low emissions, and reduced water use compared to the state-of-the-art ammonia-based and amine technologies. The overall objective of the project was to develop and test a solvent-based CO 2 capture technology that can capture CO 2 from existing or new pulverized coal (PC) power plants at low cost. Our specific goal was to test SRI’s newly developed MSP at the large bench-scale level to demonstrate that the process could capture CO 2 at high efficiency (> 90%) with very high CO 2 loading (> 10 wt.%), require less than 2 GJ/tonne for solvent regeneration, and produce a CO 2 stream at high pressure with a purity > 95 vol.%. This 45-month MSP development program was designed to conduct (1) extensive test campaigns with different process flowsheet variants, and (2) detailed thermodynamic, kinetic, and process modeling. These tests and models were very important to identify any issues associated with the process in the early stages and then resolve them before moving into the next scale-up (> 1 MWe scale) testing. The technology development plan consisted of balanced experimental and process modeling activities as shown in Figure i. Such an approach reduces the risks associated with the process operability at large scales and provides capital and operating expenditure (CAPEX/OPEX) predictions with improved accuracies. Under the MSP development program at SRI, we performed an aggressive testing campaign with individual subsystems as well as integrated CO 2 capture and regeneration system to identify the best operating conditions. The project was carried out in two budget periods (BP1 & BP2).

20 FOSSIL-FUELED POWER PLANTS↗
DOE OSTI2018

Development of Mixed-Salt Technology for CO 2 Capture from Coal Power Plants (Final Report)

SRI International (SRI), in collaboration with Stanford University, OLI Systems (OLI), Politecnico de Milano (PoliMi), and Aqueous Systems Aps (ASApS) performed a 45-month effort to develop a promising Mixed-Salt Process (MSP) for carbon dioxide capture. The MSP combines existing ammonia and potassium-carbonate technologies with improved absorption steps for rate enhancement and ammonia emission reduction and a novel selective regeneration process with a high-pressure CO 2 product to introduce a new and advanced transformational solvent-based technology. The striking advantages of the SRI MSP include: low heat of reaction, high loading of CO 2 , high-pressure regeneration of > 99% pure dry CO 2 , low sensitivity to impurities, low process cost, use of a non-degradable low-cost solvent with a very low carbon footprint for its production, low emissions, and reduced water use compared to the state-of-the-art ammonia-based and amine technologies. The overall objective of the project was to develop and test a solvent-based CO 2 capture technology that can capture CO 2 from existing or new pulverized coal (PC) power plants at low cost. Our specific goal was to test SRI’s newly developed MSP at the large bench-scale level to demonstrate that the process could capture CO 2 at high efficiency (> 90%) with very high CO 2 loading (> 10 wt.%), require less than 2 GJ/tonne for solvent regeneration, and produce a CO2 stream at high pressure with a purity > 95 vol.%. This 45-month MSP development program was designed to conduct (1) extensive test campaigns with different process flowsheet variants, and (2) detailed thermodynamic, kinetic, and process modeling. These tests and models were very important to identify any issues associated with the process in the early stages and then resolve them before moving into the next scale-up (> 1 MWe scale) testing. Such an approach reduces the risks associated with the process operability at large scales and provides capital and operating expenditure (CAPEX/OPEX) predictions with improved accuracies. Under the MSP development program at SRI, we performed an aggressive testing campaign with individual subsystems as well as integrated CO 2 capture and regeneration system to identify the best operating conditions. The project was carried out in two budget periods (BP1 & BP2).

20 FOSSIL-FUELED POWER PLANTS↗
DOE OSTI2024

Electrocatalytic nitrate reduction: controlling adsorbate affinity to tailor reaction products

Every year, Haber-Bosch nitrogen fixation to form ammonia releases immense volumes of CO2. At the same time, nitrate contamination from untreated wastewater threatens human health across the US. Development of circular processes to efficiently upgrade waste nitrate for reuse is critical to sustainably address this growing environmental hazard. Electrochemical reduction of nitrate operates at ambient temperatures and pressures, and can leverage distributed renewable energy sources and water as a hydrogen source for ammonia production. However, current catalysts lack electron efficiency in reducing nitrate versus water, lack selectivity in forming ammonia as a product, or rely on expensive rare metals, making widespread implementation unfeasible. To overcome these limitations, this proposal seeks a mechanistic understanding of nitrate electrochemical reduction on earth abundant metals and their alloys, with the goal of identifying active-site properties that improve both Faradaic efficiency and product selectivity. This insight will extend to other electrocatalytic reductive process that compete with water reduction.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2018

Drying and Rainfall Shape the Structure and Functioning of Nitrifying Microbial Communities in Riverbed Sediments

Non-flow periods in fluvial ecosystems are a global phenomenon. Streambed drying and rewetting by sporadic rainfalls could drive considerable changes in the microbial communities that govern stream nitrogen (N) availability at different temporal and spatial scales. We performed a microcosm-based experiment to investigate how dry period duration (DPD) (0, 3, 6, and 9 weeks) and magnitude of sporadic rewetting by rainfall (0, 4, and 21 mm applied at end of dry period) affected stocks of N in riverbed sediments, ammonia-oxidizing bacteria (AOB) and archaea (AOA) and rates of ammonia oxidation (AO), and emissions of nitrous oxide (N 2 O) to the atmosphere. While ammonium (NH 4 + ) pool size decreased, nitrate (NO 3 - ) pool size increased in sediments with progressive drying. Concomitantly, the relative and absolute abundance of AOB and, especially, AOA (assessed by 16S rRNA gene sequencing and quantitative PCR of ammonia monooxygenase genes) increased, despite an apparent decrease of AO rates with drying. An increase of N 2 O emissions occurred at early drying before substantially dropping until the end of the experiment. Strong rainfall of 21 mm increased AO rates and NH 4 + in sediments, whereas modest rainfall of 4 mm triggered a notable increase of N 2 O fluxes. Interestingly, such responses were detected only after 6 and 9 weeks of drying. Our results demonstrate that progressive drying drives considerable changes in in-stream N cycling and the associated nitrifying microbial communities, and that sporadic rainfall can modulate these effects. Our findings are particularly relevant for N processing and transport in rivers with alternating dry and wet phases – A hydrological scenario expected to become more important in the future.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

ExoReL{sup R}: A Bayesian Inverse Retrieval Framework for Exoplanetary Reflected Light Spectra

The high-contrast imaging technique is meant to provide insight into those planets orbiting several astronomical units from their host star. Space missions such as Wide-Field InfraRed Survey Telescope, Habitable Exoplanet Imaging Mission, and Large Ultra-Violet/Optical/InfraRed Surveyor will measure reflected light spectra of cold gaseous and rocky planets. To interpret these observations, we introduce ExoReL{sup R} (Exoplanetary Reflected Light Retrieval), a novel Bayesian retrieval framework to retrieve cloud properties and atmospheric structures from exoplanetary reflected light spectra. As a unique feature, it assumes a vertically nonuniform volume mixing ratio (VMR) profile of water and ammonia, and uses it to construct cloud densities. In this way, clouds and molecular mixture ratios are consistent. We apply ExoReL{sup R} on three test cases: two exoplanets (υ And e and 47 Uma b) and Jupiter. We show that we are able to retrieve the concentration of methane in the atmosphere, and estimate the position of clouds when the signal-to-noise ratio of the spectrum is higher than 15, in line with previous works. Moreover, we described the ability of our model to give a chemical identity to clouds, and we discussed whether or not we can observe this difference in the planetary reflection spectrum. Finally, we demonstrate how it could be possible to retrieve molecular concentrations (water and ammonia in this work) below the clouds by linking the nonuniform VMR profile to the cloud presence. This will help to constrain the concentration of water and ammonia unseen in direct measurements.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2017

High-mass Star Formation in the Outer Scutum–Centaurus Arm

The Outer Scutum–Centaurus (OSC) spiral arm is the most distant molecular spiral arm in the Milky Way, but until recently little was known about this structure. Discovered by Dame and Thaddeus, the OSC lies ∼15 kpc from the Galactic Center. Due to the Galactic warp, it rises to nearly 4° above the Galactic Plane in the first Galactic quadrant, leaving it unsampled by most Galactic plane surveys. Here we observe H ii region candidates spatially coincident with the OSC using the Very Large Array to image radio continuum emission from 65 targets and the Green Bank Telescope to search for ammonia and water maser emission from 75 targets. This sample, drawn from the Wide-field Infrared Survey Explorer Catalog of Galactic H ii Regions, represents every H ii region candidate near the longitude–latitude (ℓ,b) locus of the OSC. Coupled with their characteristic mid-infrared morphologies, detection of radio continuum emission strongly suggests that a target is a bona fide H ii region. Detections of associated ammonia or water maser emission allow us to derive a kinematic distance and determine if the velocity of the region is consistent with that of the OSC. Nearly 60% of the observed sources were detected in radio continuum, and more than 20% have ammonia or water maser detections. The velocities of these sources mainly place them beyond the Solar orbit. These very distant high-mass stars have stellar spectral types as early as O4. We associate high-mass star formation at 2 new locations with the OSC, increasing the total number of detected H ii regions in the OSC to 12.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2021

Economizing on Precious Metals in Three-Way Catalysts: Thermally Stable and Highly Active Single-Atom Rhodium on Cera for NO Abatement under Dry and Industrially Relevant Conditions

We show for the first time that atomically dispersed Rh cations on ceria, prepared via high-temperature atom trapping synthesis, are the active species for (CO+NO) reaction. This provides a direct link with the organometallic homogeneous Rh(I) complexes capable of catalyzing dry (CO+NO) reaction but without the stability concern. In particular, thermally stable Rh cations in 0.1wt% Rh1/CeO2 achieve full NO conversion with a TOF of ~ 330 hr-1 per Rh atom at 120 °C. Under dry conditions, the main product above 100 °C is N2 with N2O being the minor product. The presence of water promotes low-temperature activity of 0.1wt% Rh1/CeO2 starting at 50 °C with full NO conversion at ~120 °C. In the case with the wet stream, however, ammonia and nitrogen are the main products with only minor N2O amounts. NH3 formation at such low temperatures is attractive because of the potential to use this as a passive SCR system. Because of the uniformity of Rh ions on the support, we are able to observe the intermediates of (CO+NO) reaction via infrared measurements on Rh cations on zeolite and ceria. Furthermore, we show that ammonia formation correlates with the WGS activity of the material and thus, rhodium hydride Rh-H species are involved in this reaction: we detect Rh(CO)Hx species on ceria using isotopic IR measurements. These findings provide new mechanistic understanding for the catalytically active species in TWC catalysis and open up a new avenue for the synthesis of novel emissions control catalysts with 100% atom economy of ultra-expensive precious metals such as Rh.

Khivantsev, Konstantin↗
DOE OSTI2018

Using steam explosion or AFEX™ to produce animal feeds and biofuel feedstocks in a biorefinery based on sugarcane residues: Using Steam Explosion or AFEX™ to Produce Animal Feeds and Biofuel Feedstocks in a Biorefinery Based on Sugarcane Residues

Sustainable integration of biofuel (primarily bioethanol) and highly digestible livestock feed in production systems is a potential way to increase the economic returns to agriculture and simultaneously promote energy security, particularly in developing countries. In this work we evaluated the efficacy of steam explosion (StEx) and ammonia fiber expansion (AFEX™) as potential processes for improving the in vitro rumen digestibility, metabolizable energy, and ethanol yields from sugarcane crop residues (bagasse and cane leaf matter, CLM). Ammonia fiber expansion pretreatment enhanced the in vitro true digestibility and metabolizable energy content of sugarcane crop residues by 69% and 26%, respectively compared to untreated controls. On the other hand, StEx increased the true digestibility and metabolizable energy content of the sugarcane residues by 54% and 7%, respectively. Ammonia fiber expansion also increased the total nitrogen content of both sugarcane bagasse and CLM to more than 20.2 g kg -1 dry forage, a more than 230% improvement relative to untreated controls. High solid-loading enzymatic hydrolysis and fermentation of StEx- and AFEX™-pretreated sugarcane crop residues generated yields of up to 3368 and 4360 L of ethanol per hectare of sugarcane cultivated, respectively, at a biomass-degrading enzyme dosage of 20 mg protein per gram glucan. This research strongly suggests that the use of suitably pretreated sugarcane crop residues in integrated sugarcane biofuel-livestock production systems can increase the total per hectare agricultural output without increasing the area of sugarcane cultivated. In effect, this integrated approach promotes more sustainable biofuel production and increased food production while avoiding the potential for indirect land use change.

09 BIOMASS FUELS↗
DOE OSTI2019

Impacts of intentional mycoplasma contamination on CHO cell bioreactor cultures

Mycoplasma contamination events in biomanufacturing facilities can result in loss of production and costly cleanups. Mycoplasma may survive in mammalian cell cultures with only subtle changes to the culture and may penetrate the 0.2 µm filters often used in the primary clarification of harvested cell culture fluid. Culture cell-based and indicator cell-based assays that are used to detect mycoplasma are highly sensitive but can take up to 28 days to complete and cannot be used for real-time decision making during the biomanufacturing process. To support real-time measurements of mycoplasma contamination, there is a push to explore nucleic acid testing. However, cell-based methods measure growth or colony forming units and nucleic acid testing measures genome copy number; this has led to ambiguity regarding how to compare the sensitivity of the methods. In addition, the high risk of conducting experiments wherein one deliberately spikes mycoplasma into bioreactors has dissuaded commercial groups from performing studies to explore the multiple variables associated with the upstream effects of a mycoplasma contamination in a manufacturing setting. Here we studied the ability of Mycoplasma arginini to persist in a single-use, perfusion rocking bioreactor system containing a Chinese hamster ovary (CHO) DG44 cell line expressing a model monoclonal immunoglobulin G1 (IgG1) antibody. We examined M. arginini growth and detection by culture methods, as well as the effects of M. arginini on mammalian cell health, metabolism, and productivity. We compared process parameters and controls normally measured in bioreactors including dissolved oxygen, gas mix, and base addition to maintain pH, to examine parameter changes as potential indicators of contamination. Our work showed that M. arginini affects CHO cell growth profile, viability, nutrient consumption, oxygen use, and waste production at varying timepoints after M. arginini introduction to the culture. Importantly, how the M. arginini contamination impacts the CHO cells is influenced by the concentration of CHO cells and rate of perfusion at the time of M. arginini spike. Careful evaluation of dissolved oxygen, pH control parameters, ammonia, and arginine over time may be used to indicate Mycoplasma contamination events in biomanufacturing facilities can result in loss of production and costly cleanups. Mycoplasma may survive in mammalian cell cultures with only subtle changes to the culture and may penetrate the 0.2 µm filters often used in the primary clarification of harvested cell culture fluid. Culture cell-based and indicator cell-based assays that are used to detect mycoplasma are highly sensitive but can take up to 28 days to complete and cannot be used for real-time decision making during the biomanufacturing process. To support real-time measurements of mycoplasma contamination, there is a push to explore nucleic acid testing. However, cell-based methods measure growth or colony forming units and nucleic acid testing measures genome copy number; this has led to ambiguity regarding how to compare the sensitivity of the methods. In addition, the high risk of conducting experiments wherein one deliberately spikes mycoplasma into bioreactors has dissuaded commercial groups from performing studies to explore the multiple variables associated with the upstream effects of a mycoplasma contamination in a manufacturing setting. Here we studied the ability of Mycoplasma arginini to persist in a single-use, perfusion rocking bioreactor system containing a Chinese hamster ovary (CHO) DG44 cell line expressing a model monoclonal immunoglobulin G1 (IgG1) antibody. We examined M. arginini growth and detection by culture methods, as well as the effects of M. arginini on mammalian cell health, metabolism, and productivity. We compared process parameters and controls normally measured in bioreactors including dissolved oxygen, gas mix, and base addition to maintain pH, to examine parameter changes as potential indicators of contamination. Our work showed that M. arginini affects CHO cell growth profile, viability, nutrient consumption, oxygen use, and waste production at varying timepoints after M. arginini introduction to the culture. Importantly, how the M. arginini contamination impacts the CHO cells is influenced by the concentration of CHO cells and rate of perfusion at the time of M. arginini spike. Careful evaluation of dissolved oxygen, pH control parameters, ammonia, and arginine over time may be used to indicate Mycoplasma contamination events in biomanufacturing facilities can result in loss of production and costly cleanups. Mycoplasma may survive in mammalian cell cultures with only subtle changes to the culture and may penetrate the 0.2 µm filters often used in the primary clarification of harvested cell culture fluid. Culture cell-based and indicator cell-based assays that are used to detect mycoplasma are highly sensitive but can take up to 28 days to complete and cannot be used for real-time decision making during the biomanufacturing process. To support real-time measurements of mycoplasma contamination, there is a push to explore nucleic acid testing. However, cell-based methods measure growth or colony forming units and nucleic acid testing measures genome copy number; this has led to ambiguity regarding how to compare the sensitivity of the methods. In addition, the high risk of conducting experiments wherein one deliberately spikes mycoplasma into bioreactors has dissuaded commercial groups from performing studies to explore the multiple variables associated with the upstream effects of a mycoplasma contamination in a manufacturing setting. Here we studied the ability of Mycoplasma arginini to persist in a single-use, perfusion rocking bioreactor system containing a Chinese hamster ovary (CHO) DG44 cell line expressing a model monoclonal immunoglobulin G1 (IgG1) antibody. We examined M. arginini growth and detection by culture methods, as well as the effects of M. arginini on mammalian cell health, metabolism, and productivity. We compared process parameters and controls normally measured in bioreactors including dissolved oxygen, gas mix, and base addition to maintain pH, to examine parameter changes as potential indicators of contamination. Our work showed that M. arginini affects CHO cell growth profile, viability, nutrient consumption, oxygen use, and waste production at varying timepoints after M. arginini introduction to the culture. Importantly, how the M. arginini contamination impacts the CHO cells is influenced by the concentration of CHO cells and rate of perfusion at the time of M. arginini spike. Careful evaluation of dissolved oxygen, pH control parameters, ammonia, and arginine over time may be used to indicate mycoplasma contamination in CHO cell cultures in a bioreactor before a read-out from a traditional method.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2014

The effect of alkaline pretreatment methods on cellulose structure and accessibility

The effects of different alkaline pretreatments on cellulose structural features and accessibility are compared and correlated with the enzymatic hydrolysis of Populus . The pretreatments are shown to modify polysaccharides and lignin content to enhance the accessibility for cellulase enzymes. The highest increase in the cellulose accessibility was observed in dilute sodium hydroxide, followed by methods using ammonia soaking and lime (Ca(OH) 2 ). The biggest increase of cellulose accessibility occurs during the first 10 min of pretreatment, with further increases at a slower rate as severity increases. Low temperature ammonia soaking at longer residence times dissolved a major portion of hemicellulose and exhibited higher cellulose accessibility than high temperature soaking. Moreover, the most significant reduction of degree of polymerization (DP) occurred for dilute sodium hydroxide (NaOH) and ammonia pretreated Populus samples. The study thus identifies important cellulose structural features and relevant parameters related to biomass recalcitrance.

09 BIOMASS FUELS↗
DOE OSTI2021

Sulfur-doped graphene anchoring of ultrafine Au 25 nanoclusters for electrocatalysis

The biggest challenge of exploring the catalytic properties of under-coordinated nanoclusters is the issue of stability. We demonstrate herein that chemical dopants on sulfur-doped graphene (S-G) can be utilized to stabilize ultrafine (sub-2 nm) Au 25 (PET)18 clusters to enable stable nitrogen reduction reaction (NRR) without significant structural degradation. The Au 25 @S-G exhibits an ammonia yield rate of 27.5μgNH 3 ∙ mg Au -1 ∙ h -1 at -0.5 V with faradic efficiency of 2.3%. More importantly, the anchored clusters preserve ~ 80% NRR activity after four days of continuous operation, a significant improvement over the 15% remaining ammonia production rate for clusters loaded on undoped graphene tested under the same conditions. Isotope labeling experiments confirmed the ammonia was a direct reaction product of N 2 feeding gas instead of other chemical contaminations. Ex-situ X-ray photoelectron spectroscopy and X-ray absorption near-edge spectroscopy of post-reaction catalysts reveal that the sulfur dopant plays a critical role in stabilizing the chemical state and coordination environment of Au atoms in clusters. Further ReaxFF molecular dynamics (RMD) simulation confirmed the strong interaction between Au nanoclusters (NCs) and S-G. Furthermore, this substrate-anchoring process could serve as an effective strategy to study ultrafine nanoclusters’ electrocatalytic behavior while minimizing the destruction of the under-coordinated surface motif under harsh electrochemical reaction conditions.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2016

Charging of Proteins in Native Mass Spectrometry

Factors that influence the charging of protein ions formed by electrospray ionization from aqueous solutions in which proteins have native structures and function were investigated. Protein ions ranging in molecular weight from 12.3 to 79.7 kDa and pI values from 5.4 to 9.6 were formed from different solutions and reacted with volatile bases of gas-phase basicities higher than that of ammonia in the cell of a Fourier-transform ion cyclotron resonance mass spectrometer. The charge-state distribution of cytochrome c ions formed from aqueous ammonium or potassium acetate is the same. Moreover, ions formed from these two solutions do not undergo proton transfer to 2-fluoropyridine, which is 8 kcal/mol more basic than ammonia. These results provide compelling evidence that proton transfer between ammonia and protein ions does not limit protein ion charge in native electrospray ionization. Both circular dichroism and ion mobility measurements indicate that there are differences in conformations of proteins in pure water and aqueous ammonium acetate, and these differences can account for the difference in the extent of charging and proton-transfer reactivities of protein ions formed from these solutions. The extent of proton transfer of the protein ions with higher gas-phase basicity bases trends with how closely the protein ions are charged to the value predicted by the Rayleigh limit for spherical water droplets approximately the same size as the proteins. These results indicate that droplet charge limits protein ion charge in native mass spectrometry and are consistent with these ions being formed by the charged residue mechanism.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Semi-Targeted Analysis of Complex Matrices by ESI FT-ICR MS or How an Experimental Bias may be Used as an Analytical Tool

Ammonia is well suited to favor deprotonation process in electrospray ionization mass spectrometry (ESI-MS) to increase the formation of [M – H]{sup –}. Nevertheless, NH{sub 3} may react with carbonyl compounds (aldehyde, ketone) and bias the composition description of the investigated sample. This is of significant importance in the study of complex mixture such as oil or bio-oil. To assess the ability of primary amines to form imines with carbonyl compounds during the ESI-MS process, two aldehydes (vanillin and cinnamaldehyde) and two ketones (butyrophenone and trihydroxyacetophenone) have been infused in an ESI source with ammonia and two different amines (aniline and 3-chloronaniline). The (+) ESI-MS analyses have demonstrated the formation of imine whatever the considered carbonyl compound and the used primary amine, the structure of which was extensively studied by tandem mass spectrometry. Thus, it has been established that the addition of ammonia, in the solution infused in an ESI source, may alter the composition description of a complex mixture and leads to misinterpretations due to the formation of imines. Nevertheless, this experimental bias can be used to identify the carbonyl compounds in a pyrolysis bio-oil. As we demonstrated, infusion of the bio-oil with 3-chloroaniline in ESI source leads to specifically derivatized carbonyl compounds. Thanks to their chlorine isotopic pattern and the high mass measurement accuracy, (+) ESI Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) unambiguously highlighted them from the numerous C{sub x}H{sub y}O{sub z} bio-oil components. These results offer a new perspective into the detailed molecular structure of complex mixtures such as bio-oils. .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Influence of catalyst synthesis method on selective catalytic reduction (SCR) of NO by NH 3 with V 2 O 5 -WO 3 /TiO 2 catalysts

We compared the molecular structures, surface acidity and catalytic activity for NO/NH 3 /O 2 SCR of V 2 O 5 -WO 3 /TiO 2 catalysts for two different synthesis methods: co-precipitation of aqueous vanadium and tungsten oxide precursors with TiO(OH) 2 and by incipient wetness impregnation of the aqueous precursors on a reference crystalline TiO 2 support (P25; primarily anatase phase). Bulk analysis by XRD showed that co-precipitation results in small and/or poorly ordered TiO 2 (anatase) particles and that VO x and WO x do not form solid solutions with the bulk titania lattice. Surface analysis of the co-precipitated catalyst by High Sensitivity-Low Energy Ion Scattering (HS-LEIS) confirms that the VO x and WO x are surface segregated for the co-precipitated catalysts. In situ Raman and IR spectroscopy revealed that the vanadium and tungsten oxide components are present as surface mono-oxo O = VO 3 and O = WO 4 sites on the TiO 2 supports. Co-precipitation was shown for the first time to also form new mono-oxo surface VO 4 and WO 4 sites that appear to be anchored at surface defects of the TiO 2 support. IR analysis of chemisorbed ammonia showed the presence of both surface NH 3 * on Lewis acid sites and surface NH 4 +* on Brønsted acid sites. TPSR spectroscopy demonstrated that the specific SCR kinetics was controlled by the redox surface VO 4 species and that the surface kinetics was independent of TiO 2 synthesis method or presence of surface WO 5 sites. SCR reaction studies revealed that the surface WO5 sites possess minimal activity below ~325 °C and their primary function is to increase the adsorption capacity of ammonia. A relationship between the SCR activity and surface acidity was not found. The SCR reaction is controlled by the surface VO 4 sites that initiate the reaction at ~200 °C. The co-precipitated catalysts were always more active than the corresponding impregnated catalysts. Finally, we ascribe the higher activity of the co-precipitated catalysts to the presence of the new surface WO x sites associated surface defects on the TiO 2 support that increase the ammonia adsorption capacity.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Coupling AFEX and steam-exploded sugarcane residue pellets with a room temperature CIIII-activation step lowered enzyme dosage requirements for sugar conversion

In this study, the potential integration of steam explosion (StEx) and ammonia fiber expansion (AFEX) with existing sugar/ethanol mills to form decentralized pre-processing depots was explored. Both StEx and AFEX pretreatment facilitated the production of sugarcane bagasse (SCB) and cane leaf matter (CLM) pellets with significantly higher bulk density, mechanical durability, and hydrophobicity relative to their untreated biomass pellet controls. However, ethanol production from standalone StEx and AFEX-treated SCB and CLM pellets required enzyme dosages greater than 21 mg/g glucan to achieve enzymatic hydrolysis sugar yields of 75% and ethanol titres greater than 40 g.L -1 . Coupling AFEX-treated SCB or CLM pellets with a room temperature CIII I -activation step using liquid ammonia lowered enzyme dosage requirements by more than 50% without affecting ethanol titers and production yields (greater than300 L per Mg residual dry matter raw dry biomass (RDM)). In contrast, treating StEx-treated pellets with CIIII-activation using liquid ammonia did not result in similar enzyme dosage reductions, due to pseudo-lignin formation, leading to enzyme deactivation and/or lignin blockage that retarded enzymatic hydrolysis at low enzyme dosages. A gross energy conversion assessment revealed that low enzyme dosage (3-4 mg enzyme/g RDM) ethanol and electricity co-production from AFEX and CIII I -activated SCB and CLM can recover up to 73% of the energy in the untreated biomass, compared to 54% recovered by StEx and CIII I -activation. The results from this work suggest that StEx or AFEX based pre-processing depots can produce dense and mechanically durable biomass pellets. The AFEX-treated pellets can be easily upgraded using a room temperature CIII I -activation step at the biorefinery to significantly reduce bioconversion enzymes.

42 ENGINEERING↗
DOE OSTI2022

An experimental and modeling study on auto-ignition kinetics of ammonia/methanol mixtures at intermediate temperature and high pressure

A rapid compression machine (RCM) has been applied to measure the ignition delay times of NH 3 /CH 3 OH mixtures covering pressures of 20 and 40 bar, equivalence ratios of 0.5, 1.0 and 2.0, and temperatures between 845 and 1100 K. Here the measurements show that the NH 3 /CH 3 OH mixtures become more reactive with increasing methanol addition. Addition of merely 1% (molar basis) of CH 3 OH to NH 3 lowers the ignition temperature around 100 K at 40 bar in comparison to pure NH 3 . The ignition delay is a complex function of fuel mixture and stoichiometry. For the 1% CH 3 OH mixture, the leaner mixtures are more reactive, while the reverse trend is found for mixtures with 5%, 20% and pure CH 3 OH. Analysis of the pressure profiles shows three distinct ignition modes for NH 3/ CH 3 OH mixtures, facilitated by the pre-ignition heat release from NH 3 consumption. A detailed mechanism for ignition of NH 3 /CH 3 OH fuel blends has been developed, capable of reproducing the ignition behavior of mixtures with reasonable accuracy. A subset for amine / methanol interactions was established, with rate constants for the key reaction between NH 2 and CH 3 OH calculated from ab initio theory. A sensitivity analysis indicates that the critical reactions during the auto-ignition process vary with the CH 3 OH mole fraction in the fuel. The ammonia chemistry, namely NH 2 + NO, NH2 + NO 2 and NH 2 + HO 2 , is dominant for the mixture with 1% CH 3 OH, while the reactions related to CH 3 OH and H 2 O 2 are more important for the 20% CH 3 OH mixture. The interaction between ammonia and methanol shows a more prominent effect on auto-ignition for mixtures with 5% CH 3 OH in fuel as compared to those with 1% and 20% CH 3 OH. According to the modeling results, methanol addition is found to enrich the O/H radical pool, consuming ammonia and promoting auto-ignition through different reaction pathways.

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

Hydrocarbon-based membranes cost-effectively manage species transport and increase performance in thermally regenerative batteries

Low-temperature heat (T<130°C) can be utilized by thermally regenerative batteries (TRBs) for power production, allowing the thermal energy to be converted to storable chemical potential energy. However, TRBs suffer from high ohmic losses and ammonia crossover, which has slowed their development. In this study, we examined how the use of six different membranes influenced TRB performance, determined the most influential membrane parameters, and identified promising membrane candidates that cost-effectively increase TRB performance. Of the six membranes examined, an inexpensive, hydrocarbon CEM (Selemion CMVN) had low ammonia crossover without compromising resistance, resulting in good performance across all metrics studied. A thin anion exchange membrane (Sustainion, 50 microns) showed a high peak power density of 82 mW cm –2 due to low resistance, but the average power density and energy density were low due to high ammonia flux. Full discharge curves using Selemion CMVN provided an average power density of 26 ± 7 mW cm –2 with an energy density of 2.9 Wh L –1 , which were large improvements on previous TRBs. A techno-economic analysis showed that Selemion CMVN had the lowest levelized cost of storage ($410 per MWh) at an applied current density of 50 mA cm –2 .

25 ENERGY STORAGE↗
DOE OSTI2022

Stoichiometric metal nitration based novel green synthesis of mesoporous metal oxides and their enhanced heterogeneity

Here, in this work, a general and novel method for the green synthesis of mesoporous metal oxides via stoichiometric metal nitration has been demonstrated. Pluronic surfactants and their effect on synthesis procedures in terms of surface area have been experimentally studied in detail. Contrary to the traditional synthesis procedure, water has been utilized as the solvent and in several cases, such as tin oxide, manganese oxide, aluminum oxide, antimony oxide, zinc oxide, cobalt oxide, copper oxide, yttrium oxide, lanthanum oxide, and silver either the highest or comparable surface areas have been successfully synthesized. Through XRD, and TEM, all materials were observed to be crystalline except silver and magnesium oxide. SEM shows that with an increase in surfactant molar mass agglomeration decreases. Ammonia chemisorption on acidic materials gives quantitative amounts of ammonia chemical bonding with catalysts, whereas carbon dioxide chemisorption gives a quantitative value of CO 2 chemical binding with basic sites. As high as 1901.8 μmol/g and 994.6 μmol/g ammonia chemisorption values for oxides of vanadium and tin were achieved. Amphoteric materials give both acidic and basic enhanced adsorption. Finally, all synthesized materials are studied under organic catalytic transformations. Benzyl bromide is theoretically more active compared with benzylamine and benzyl alcohol which was also experimentally shown through the conversion.

36 MATERIALS SCIENCE↗