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At least 721 records · Page 40

All sources NASA NTRS DOE OSTI

DOE OSTI2021

Effects of Lithium-ion Battery Recycling Wastes on Ammonia-Oxidizing Bacteria

Increased demand for lithium-ion batteries (LIB) necessitates development of effective recycling methods for critical battery materials. Oak Ridge National Laboratory (ORNL) is exploring membrane solvent extraction (MSX) for the hydrometallurgical recycling of LIB materials. In this study, waste from MSX was investigated for its impact on the ammonia-oxidizing organism, Nitrosomonas europaea—a model organism for nitrogen removal during wastewater treatment. It was found that Raffinate 4 from ORNL was inhibitory to the growth and nitrite production of N. europaea, likely due to its nickel content. Further investigation is currently underway.

99 GENERAL AND MISCELLANEOUS↗

DOE OSTI2020

Uranium Partitioning upon Ammonia Gas Treatment on Phyllosilicate Minerals

In the past, > 200,000 kg of U was released to the Hanford Site vadose zone from disposal and leakage of waste byproducts from plutonium production during World War II and the Cold War (Zachara et al., 2007). U is highly mobile due to the presence of carbonates and oxidizing conditions, with K{sub d} of 0.1 - 8 mL/g at the site (Zachara et al., 2007; Szecsody et al., 2013; Serne et al., 2008). NH{sub 3} (gas) injection is being investigated as a remediation technique as it is an in situ method that will not introduce additional liquid that could drive contaminants deeper into vadose zone towards groundwater. Objectives: To understand the impact of alkaline injection on geochemical processes in the Hanford Site vadose zone, including: 1)Long-term fate of uranium (U); 2)Dissolution and re-precipitation of secondary minerals. Apparent K{sub d}'s increase significantly with NH{sub 3} gas treatment, especially for six-month aging. - K{sub d} decreases after aeration, primarily due to U desorption at lower pH. U removal is still significantly greater than natural conditions (K{sub d} < 8 vs. > 100 mL/g). - Three-day aeration has higher loading than six-month after ammonia gas treatment and aeration. However, significantly greater desorption of U occurs with aeration in the six-month aged sample potentially due to transformation into different, more soluble solid phases with longer term aging. - U removal is primarily due to (1) co-precipitation of U with secondary minerals and (2) adsorption to minerals' surface, although further research is required to identify dominant mechanisms. Future experiments will focus on garnering a better understanding of the solid phase U speciation. Solids will be characterized using SEM-EDS, EMPA, XPS, XAFS, and TEM to better understand the effects of basic treatments on initial minerals and formation of secondary precipitates.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2015

Ammonia and methane dairy emissions in the San Joaquin Valley of California from individual feedlot to regional scale

Agricultural ammonia (NH 3 ) emissions are highly uncertain, with high spatiotemporal variability and a lack of widespread in situ measurements. Regional NH 3 emission estimates using mass balance or emission ratio approaches are uncertain due to variable NH 3 sources and sinks as well as unknown plume correlations with other dairy source tracers. We characterize the spatial distributions of NH 3 and methane (CH 4 ) dairy plumes using in situ surface and airborne measurements in the Tulare dairy feedlot region of the San Joaquin Valley, California, during the NASA Deriving Information on Surface conditions from Column and Vertically Resolved Observations Relevant to Air Quality 2013 field campaign. Surface NH 3 and CH 4 mixing ratios exhibit large variability with maxima localized downwind of individual dairy feedlots. The geometric mean NH 3 :CH 4 enhancement ratio derived from surface measurements is 0.15 ± 0.03 ppmv ppmv –1 . Individual dairy feedlots with spatially distinct NH 3 and CH 4 source pathways led to statistically significant correlations between NH 3 and CH 4 in 68% of the 69 downwind plumes sampled. At longer sampling distances, the NH 3 :CH 4 enhancement ratio decreases 20–30%, suggesting the potential for NH 3 deposition as a loss term for plumes within a few kilometers downwind of feedlots. Aircraft boundary layer transect measurements directly above surface mobile measurements in the dairy region show comparable gradients and geometric mean enhancement ratios within measurement uncertainties, even when including NH 3 partitioning to submicron particles. Individual NH 3 and CH 4 plumes sampled at close proximity where losses are minimal are not necessarily correlated due to lack of mixing and distinct source pathways. As a result, our analyses have important implications for constraining NH 3 sink and plume variability influences on regional NH 3 emission estimates and for improving NH 3 emission inventory spatial allocations.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2025

Magnesium‐Mediated Electrochemical Synthesis of Ammonia

Metal-mediated electrochemical synthesis of ammonia (NH3) is a promising method to activate N2 at room temperature. While a Li-mediated approach has been optimized to produce NH3 at high current density and selectivity, Li's scarcity and its highly negative plating potential limit scalability and energy efficiency. Alternative mediators have been proposed, but only Ca has shown some promise, achieving ≈50% Faradaic efficiency (FE), though requiring voltages beyond -3 V. Here, we report a Mg-mediated nitrogen reduction reaction (Mg-NRR), where N2 is activated on Mg to form Mg3N2, followed by protolysis to release NH3 and regenerate Mg. A notable NH3 FE of 25.28 ± 3.80% is achieved at a current density of -45 mA cm-2, corresponding to an NH3 partial current density of -11.30 ± 1.77 mA cm-2 under 6 bar N2. Isotope-labeled experiments confirm that NH3 originates from N2, with similar FE (25.15 ± 1.01%). Importantly, NH3 production is demonstrated at a total cell potential as low as -3 V. This Li-free Mg-NRR system offers key advantages, including lower energy input and use of earth-abundant materials, making it a scalable route for sustainable NH3 synthesis.

Goyal, Ishita↗

DOE OSTI2020

A Surface‐Strained and Geometry‐Tailored Nanoreactor that Promotes Ammonia Electrosynthesis

Abstract A surface‐strained and geometry‐optimized TiO 2 nanoreactor enhances the performance of electrocatalytic nitrogen fixation. The nanotubular confinement allows spatial regulation of the mass transport of nitrogen during the NRR process and offers an enlarged surface area, thus boosting the ammonia production with high selectivity. Both experimental and theoretical evidence support strained Ti 3+ sites, demonstrating a more favorable pathway for the N 2 activation and selective NH 3 production with a faster kinetic rate than the pristine TiO 2 . The TiO 2 ‐based nanoreactor with surface and bulk structure tailoring delivered an NH 3 yield rate up to 5.50 μg h −1 cm −2 (16.67 μg h −1 mg cat −1 ) and high faradaic efficiency of 26 % under ambient aqueous conditions. Our findings highlight the concept of lattice strain and geometry modified nanoreactors, which will have broad implications in the renewable energy catalysis and electrosynthesis of valuable products.

Li, Panpan↗

DOE OSTI2023

Supramolecular Enhancement of Electrochemical Nitrate Reduction Catalyzed by Cobalt Porphyrin Organic Cages for Ammonia Electrosynthesis in Water**

Abstract The electrochemical nitrate (NO 3 − ) reduction reaction (NO 3 RR) to ammonia (NH 3 ) represents a sustainable approach for denitrification to balance global nitrogen cycles and an alternative to traditional thermal Haber‐Bosch processes. Here, we present a supramolecular strategy for promoting NH 3 production in water from NO 3 RR by integrating two‐dimensional (2D) molecular cobalt porphyrin ( CoTPP ) units into a three‐dimensional (3D) porous organic cage architecture. The porphyrin box CoPB‐C8 enhances electrochemical active site exposure, facilitates substrate–catalyst interactions, and improves catalyst stability, leading to turnover numbers and frequencies for NH 3 production exceeding 200,000 and 56 s −1 , respectively. These values represent a 15‐fold increase in NO 3 RR activity and 200‐mV improvement in overpotential for the 3D CoPB‐C8 box structure compared to its 2D CoTPP counterpart. Synthetic tuning of peripheral alkyl substituents highlights the importance of supramolecular porosity and cavity size on electrochemical NO 3 RR activity. These findings establish the incorporation of 2D molecular units into 3D confined space microenvironments as an effective supramolecular design strategy for enhancing electrocatalysis.

An, Lun↗

DOE OSTI2018

Ambient Electrosynthesis of Ammonia: Electrode Porosity and Composition Engineering

Ammonia, a key precursor for fertilizer production, convenient hydrogen carrier, and emerging clean fuel, plays a pivotal role in sustaining life on Earth. Currently, the main route for NH 3 synthesis is by the heterogeneous catalytic Haber–Bosch process (N 2 +3 H 2 →2 NH 3 ), which proceeds under extreme conditions of temperature and pressure with a very large carbon footprint. Herein we report that a pristine nitrogen–doped nanoporous graphitic carbon membrane (NCM) can electrochemically convert N 2 into NH 3 in an acidic aqueous solution under ambient conditions. The Faradaic efficiency and rate of production of NH 3 on the NCM electrode reach 5.2 % and 0.08 g m –2 h –1 , respectively. Functionalization of the NCM with Au nanoparticles dramatically enhances these performance metrics to 22 % and 0.36 gm –2 h –1 , respectively. In conclusion, as this system offers the potential to be scaled to industrial levels it is highly likely that it might displace the century-old Haber–Bosch process.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2020

A Surface-Strained and Geometry-Tailored Nanoreactor that Promotes Ammonia Electrosynthesis

A surface-strained and geometry-optimized TiO 2 nanoreactor enhances the performance of electrocatalytic nitrogen fixation. The nanotubular confinement allows spatial regulation of the mass transport of nitrogen during the NRR process and offers an enlarged surface area, thus boosting the ammonia production with high selectivity. Both experimental and theoretical evidence support strained Ti 3+ sites, demonstrating a more favorable pathway for the N 2 activation and selective NH 3 production with a faster kinetic rate than the pristine TiO 2 . The TiO 2 -based nanoreactor with surface and bulk structure tailoring delivered an NH 3 yield rate up to 5.50 μg h -1 cm -2 (16.67 μg h -1 mg cat -1 ) and high faradaic efficiency of 26 % under ambient aqueous conditions. Furthermore, our findings highlight the concept of lattice strain and geometry modified nanoreactors, which will have broad implications in the renewable energy catalysis and electrosynthesis of valuable products.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Supramolecular Enhancement of Electrochemical Nitrate Reduction Catalyzed by Cobalt Porphyrin Organic Cages for Ammonia Electrosynthesis in Water**

An, Lun↗

DOE OSTI2017

Development of rapid bioconversion with integrated recycle technology for ethanol production from extractive ammonia pretreated corn stover

ABSTRACT High enzyme loading and low productivity are two major issues impeding low cost ethanol production from lignocellulosic biomass. This work applied rapid bioconversion with integrated recycle technology (RaBIT) and extractive ammonia (EA) pretreatment for conversion of corn stover (CS) to ethanol at high solids loading. Enzymes were recycled via recycling unhydrolyzed solids. Enzymatic hydrolysis with recycled enzymes and fermentation with recycled yeast cells were studied. Both enzymatic hydrolysis time and fermentation time were shortened to 24 h. Ethanol productivity was enhanced by two times and enzyme loading was reduced by 30%. Glucan and xylan conversions reached as high as 98% with an enzyme loading of as low as 8.4 mg protein per g glucan. The overall ethanol yield was 227 g ethanol/kg EA‐CS (191 g ethanol/kg untreated CS). Biotechnol. Bioeng. 2017;114: 1713–1720. © 2017 Wiley Periodicals, Inc.

Jin, Mingjie↗

DOE OSTI2020

Manipulating the Geometric and Electronic Structures of Manganese Nitrides for Ammonia Synthesis

Abstract Manganese (Mn) nitrides are important nitrogen (N) carriers for small‐scale intermittent ammonia (NH 3 ) synthesis. However, only 3∼8 % of lattice N are converted into NH 3 . In this study, the geometric and electronic structures of well‐defined Mn 4 N and Mn 2 N lattices were altered using transition metal heteroatoms (Cr, Fe, Co, Ni, Mo) to understand the driving force behind lattice N diffusion and extraction. Density Functional Theory (DFT) revealed that the binding of early hydrogenation product (NH) follows a linear relationship with lattice N over a wide range of close‐packed surfaces. But, the binding of NH 2 and NH 3 are more sensitive to the geometric and electronic structures. Further, the chemical bonding can be quantitatively characterized with the covalency derived from Crystal Orbital Hamiltonian Population (COHP). In the Eley Rideal‐Mars van Krevelan pathway, the overall NH 3 formation free energy ( ) and lattice N diffusion barrier ( ) are the respective thermodynamic and kinetic determining factors. Aided by a rate‐determining step (RDS) model, Mn 4 N modified with Fe, Co, Ni single‐atom dopants all show enhanced rates for NH 3 formation.

Shan, Nannan↗

DOE OSTI2020

Chemical Looping of Manganese to Synthesize Ammonia at Atmospheric Pressure: Sodium as Promoter

Abstract Affordable synthetic ammonia (NH 3 ) enables the production of nearly half of the food we eat and is emerging as a renewable energy carrier. Sodium‐promoted chemical looping NH 3 synthesis at atmospheric pressure using manganese (Mn) is here demonstrated. The looping process may be advantageous when inexpensive renewable hydrogen from electrolysis is available. Avoiding the high pressure of the Haber‐Bosch process by chemical looping using earth‐abundant materials may reduce capital cost, facilitate intermittent operation, and allow operation in geographic areas where infrastructure is less sophisticated. At this early stage, the data suggest that 0.28 m 3 of a 50 % porosity solid Mn bed may suffice to produce 100 kg NH 3 per day by chemical looping, with abundant opportunities for improvement.

Aframehr, Wrya Mohammadi↗

DOE OSTI2017

Understanding the Changes to Biomass Surface Characteristics after Ammonia and Organosolv Pretreatments by Using Time-of-Flight Secondary-Ion Mass Spectrometry (TOF-SIMS)

Surface characteristic changes to poplar after ammonia and organosolv pretreatments were investigated by means of time-of-flight secondary-ion mass spectrometry (TOF-SIMS) analysis. Whereas normalized total polysaccharides and lignin contents on the surface differed from bulk chemical compositions, the surface cellulose ions detected by TOF-SIMS showed the same value trend as the cellulose content in the biomass. In addition, the lignin syringyl/guaiacyl ratio according to TOF-SIMS results showed the same trend as the ratio measured by means of NMR spectroscopic analysis, even though the ratio scales for each method were different. A similar correlation was determined between the surface cellulose and glucose release after enzymatic hydrolysis. Lastly, these results demonstrate that surface characterization using TOF-SIMS can provide important information about the effects of pretreatment on biomass properties and its hydrolysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2019

Efficient Electrocatalytic Synthesis of Ammonia from Water and Air in a Membrane‐Free Cell: Confining the Iron Oxide Catalyst to the Cathode

Ammonia is critical for food and chemical production; however, NH 3 synthesis is one of the largest industrial greenhouse gas producers. We report a path to an exceptionally high rate (2.3 × 10 –9 mol of NH 3 s –1 cm –2 ), CO 2 free NH 3 electrosynthesis from H 2 O and air under ambient electrolysis conditions (60 °C, 1 atm). Iron oxide (dispersed in hydroxide electrolyte) catalyzed NH 3 synthesis is probed at intermediate temperature (20–200 °C) and pressure (1–10 atm) with Monel mesh electrodes. Iron calcination preparation of the iron oxide catalyst is optimized by size, and then physically constrained to the reactive domain of the electrolysis cell cathode through use of mesh electrodes at even lower temperatures, allowing for an ambient, preferred electrosynthesis. These novel constraints enhance NH 3 catalyst utilization at low temperature and open future pathways to the addition of ion‐specific membranes to the high rate NH 3 synthesis cell.

Liu, Xinye↗

DOE OSTI2021

Renewable hydrogen and ammonia for combined heat and power systems in remote locations: Optimal design and scheduling

Abstract Using hydrogen (H ) and ammonia (NH ) for renewable energy storage has the potential to enable economical power and heat supply with high renewable penetrations, especially in remote locations which are characterized by high energy costs. In this work we assess the economic competitiveness of renewable combined heat and power (CHP) systems in Mahaka HI, Nantucket MA, and Northwest Arctic Borough (NWAB) AK by optimally designing these systems for scenarios in which power and heat can be purchased over a range of historical energy prices as well as when 100% renewable supply is required. We use a combined optimal design and scheduling model which minimizes annualized net present cost by determining optimal technology selection and size simultaneously with optimal schedules for each period of a system operating horizon aggregated from full year hourly resolution data via a consecutive temporal clustering algorithm. We find that renewable generation meets at least 85% of power demands and 75% of heat demands under the lowest energy prices investigated. Higher conventional energy prices lead to increased renewable penetration which is facilitated by renewable NH as a seasonal energy storage medium, as are 100% renewable CHP systems. NH is used for power generation with heat cogeneration in all three locations, as well as directly for heating in NWAB. On an annual cost basis, NH ‐enabled 100% renewable CHP is only 3% more expensive in Mahaka and NWAB than systems which can purchase energy at the lowest prices, while it is 15% more expensive in Nantucket.

Palys, Matthew J.↗

DOE OSTI2019

Fertilizer timing affects nitrous oxide, carbon dioxide, and ammonia emissions from soil

The impact of interactions between management and climate on nitrous oxide (N 2 O), carbon dioxide (CO 2 ), and ammonia (NH 3 ) emissions are not well understood. This study quantified the effect of urea fertilizer application timing on inorganic N movement, immobilization, and the gaseous emissions of N 2 O-N, CO 2 -C, and NH 3 -N. Urea was applied once, at two rates (0 and 224 kg ha -1 ) on six dates (early fall, 20 Sept. 2017; mid-fall, 11 Oct. 2017; early winter, 1 Nov. 2017; early spring, 1 May 2018; mid-spring, 22 May 2018; and early summer, 12 June 2018). Gaseous emissions, soil temperature, and soil moisture were measured every 4 h for 21 consecutive days following urea application. Changes in soil inorganic N contents were used to determine the amount of inorganic N remaining in the soil, nitrification, immobilization/fixation, and leaching. For all fertilizer application dates, the cumulative fertilizer derived N 2 O-N emissions for the 21 days following application were <0.05% of the applied N. Fertilizer-derived N 2 O-N emission rates were higher than N 2 O-N emission rates in the unfertilized soil in early fall and early summer. Even though the highest net N 2 O-N emissions occurred in early spring, the application of fertilizer did not increase emissions. The highest net N 2 O-N + NH 3 -N emissions occurred in cool soils (early spring) in soils with water filled pore space (>60%). These findings indicate that intergovernmental panel on climate change (IPCC) default value of 1% of applied N for N 2 O emissions improved by considering the fertilizer application date.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2022

Atomic Molybdenum for Synthesis of Ammonia with 50% Faradic Efficiency

The electrochemical dinitrogen (N 2 ) reduction reaction (NRR) under ambient conditions has gained significant interest as an environmentally friendly alternative to the traditional Haber–Bosch process for the synthesis of ammonia (NH 3 ). However, up to now, most of the reported NRR electrocatalysts with satisfactory catalytic activities have been hindered by the large overpotential in N 2 activation. The preparation of highly efficient Mo-based NRR electrocatalyst in acidic electrolytes under ambient conditions is demonstrated here, consisting of stabilized single Mo atoms anchored on holey nitrogen-doped graphene synthesized through a convenient potassium-salt-assisted activation method. At -0.05 V versus a reversible hydrogen electrode (RHE), an electrode consisting of the resultant electrocatalyst immobilized on carbon fiber paper can attain an exceptional Faradaic efficiency of 50.2% and a NH3 yield rate of 3.6 µg h -1 mg cat -1 with low overpotentials. Density functional theory calculations further unveil that compared to the original graphene without holes, the edge coordinated Mo atoms and the existence of vacancies on holey graphene lower the overpotential of N 2 reduction, thereby promoting the NRR catalytic activity. Finally, this work could provide new guidelines for future designs in single-atom catalysis that would be beneficial to ambient N 2 fixation, and replacement of classical synthesis processes that are very energy-intensive.

36 MATERIALS SCIENCE↗

DOE OSTI2021

All-aerosol-jet-printed highly sensitive and selective polyaniline-based ammonia sensors: a route toward low-cost, low-power gas detection

In this work, we report the design and scalable fabrication of a low-cost and low-power polyaniline-based (PANI) ammonia (NH3) gas sensor on polyimide (PI) substrates using additive manufacturing techniques. The silver interdigitated electrode (IDE) arrays and conducting polymer films are printed onto PI using a direct-write technology of aerosol-jet printing. Morphological characteristics are examined by scanning electron microscopy and energy-dispersive X-ray analysis which reveal homogeneously printed PANI film on the IDE platform. The gas sensing performance is evaluated in the analytical early leak detection range of 5–1000 ppm NH3 in air as a function of both thermal (23 °C, 50 °C, 80 °C) and relative humidity (RH = 0%, 30%, 50%) exposures. The sensor exhibits sensitivity down to 5 ppm NH3 with a sub-ppm detection limit and good repeatability. We observe rapid NH3 detection at 0% RH with very extended times for equilibration and recovery. However, at both 30 and 50% RH, the room temperature response and recovery times are reduced to only about 1 min and 5 min, respectively. Experiments also reveal good sensitivity toward the analyte even at higher operating temperatures. Present results merit the practical application of aerosol-jet-printed, low-power sensors for industrial applications where low-level hazardous gas detection is essential.

36 MATERIALS SCIENCE↗