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At least 631 records · Page 35
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Catalytic Ammonia Oxidation to Dinitrogen by Hydrogen Atom Abstraction

Catalysts for the oxidation of NH 3 will be critical to utilize NH 3 as a large-scale energy carrier. Molecular complexes have not been shown to catalyze the oxidation of NH 3 to N 2 . We report Ru- catalyzed oxidation of ammonia to dinitrogen under ambient conditions using the molecular complex [Cp*Ru(P t Bu 2 N Ph 2 )( 15 NH 3 )][BAr F 4 ]. Mediating the cleavage of six N-H bonds and the formation of an N≡N bond was achieved by coupling H + and e - transfers as net hydrogen atom abstraction steps using the 2,4,6-tri- t ert-butylphenoxyl radical ( t Bu 3 ArO•) as the H atom acceptor. Employing an excess of t Bu 3 ArO• under 1 atm of NH 3 gas at 23 °C resulted in up to six turnovers. As a result, nitrogen isotopic ( 15 N) labeling studies provide mechanistic insights to confirm the N≡N bond forming step in the catalytic cycle.

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

Disordered Au Nanoclusters for Efficient Ammonia Electrosynthesis

The electrochemical nitrogen (N 2 ) reduction reaction (N 2 RR) under mild conditions is a promising and environmentally friendly alternative to the traditional Haber-Bosch process with high energy consumption and greenhouse emission for the synthesis of ammonia (NH 3 ), but high-yielding production is rendered challenging by the strong nonpolar N≡N bond in N 2 molecules, which hinders their dissociation or activation. In this study, disordered Au nanoclusters anchored on two-dimensional ultrathin Ti 3 C 2 T x MXene nanosheets are explored as highly active and selective electrocatalysts for efficient N 2 -to-NH 3 conversion, exhibiting exceptional activity with an NH 3 yield rate of 88.3±1.7 μg h –1 mg cat. –1 and a faradaic efficiency of 9.3±0.4 %. Further, a combination of in situ near-ambient pressure X-ray photoelectron spectroscopy and operando X-ray absorption fine structure spectroscopy is employed to unveil the uniqueness of this catalyst for N 2 RR. The disordered structure is found to serve as the active site for N 2 chemisorption and activation during the N 2 RR process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

A microfabricated electroosmotic pump coupled to a gas-diffusion microchip for flow injection analysis of ammonia

Here we have microfabricated two functional components toward developing a microchip flow injection analysis (FIA) system, i.e., an open-channel electroosmotic pump and a gas-diffusion chip, consisting of two microfabricated glass wafers and a porous polytetrafluoroethylene membrane. This is the first application of gas-diffusion separation in a microchip FIA system. To demonstrate the feasibility of using these two components for performing gas-diffusion FIA, we have incorporated them together with a regular FIA injection valve and a capillary electrophoresis absorbance detector in a flow injection system for determination of ammonia in environmental water samples. This system has a limit of detection of 0.10 mg L -1 NH 3 , with a good repeatability (relative standard deviation of less than 5 % for 4.0 mg L - 1 NH 3 ). We also discuss parameters affecting its performance.

42 ENGINEERING↗
DOE OSTI2019

Investigation of in situ high temperature sensor based on the direct absorption spectroscopy signal of ammonia gas for coal-fired power plant

The selective catalytic reduction and non-selective catalytic reduction (SCR/SNCR) are the most popular de-NOx processes for coal-fired power plant, where the real-time temperature is a significant parameter. A new developed tunable diode laser spectroscopy used for measuring the temperature of ammonia (NH{sub 3}) in the process of SCR/SNCR influenced by strong exhaust gas matrices CO{sub 2} and H{sub 2}O was presented in this paper. Two lines near 6605 cm{sup −1} were selected, with rather weak temperature dependency and minimal interface from CO{sub 2} and H{sub 2}O according to HITRAN12 database. A homemade heating equipment for high temperature laser spectroscopy measurement was developed based on an ARM microcontroller. The temperature calibration experiments of absorption lines were carried out at variable concentrations under different temperatures. The spectral signals of 2.5%, 3.5% and 4.5% NH{sub 3} were observed for validation of the generalization and robustness of the sensor. The calibration and validation experimental results show that the maximum measurement error and global average error of the temperature sensor with the temperature ranging from 453 to 653 K are less than 2% and 1.38%, respectively. It demonstrates that our proposed sensor with high accuracy and linearity, and can be utilized to measure the temperature in SNCR/SCR process.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2019

Reaction Mechanism and Kinetics of Boron Removal from Molten Silicon via CaO-SiO{sub 2}-CaCl{sub 2} Slag Treatment and Ammonia Injection

To improve the boron-removal efficiency of metallurgical-grade silicon by increasing the reaction rate, a combined method with the 30 mol pct CaO-23.3 mol pct SiO{sub 2}-46.7 mol pct CaCl{sub 2} slag treatment and ammonia injection at 1723 K to 1823 K was proposed. For 1 hour and at 1823 K, the maximum removal efficiency of boron was 98 pct, and the final boron concentration in silicon decreased to 1.5 ppmw by the present method without the introduction of the iron catalyst. A kinetic model was also established to clarify the reaction mechanism and rate-limiting steps of this complicated boron-removal process. In this model, the rate-limiting step is the mass transfer of boron oxide at the interface between the slag and silicon phase.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Type 2 diabetes mellitus correlates with systolic function during myocardial stress perfusion scanning with Nitrogen-13 ammonia PET

Background: The influence of type 2 diabetes mellitus (DM2) on systolic function is partially determined by the coronary vasodilator function, nevertheless, an independent effect is suspected. We evaluated the relationship between DM2 and systolic function considering PET quantitative myocardial perfusion. Methods: We analyzed 585 patients without a previous myocardial infarction referred to a rest and adenosine stress Nitrogen-13 ammonia PET. A bootstrapped multiple linear regression analysis was performed using DM2, stress myocardial blood flow (sMBF), myocardial perfusion reserve (MPR), and clinical risk factors as predictors and LVEF as the outcome variable; an interaction term was additionally investigated. Results: Two hundred and ninety male and 295 female patients (mean age 65.3 ± 9.9 and 67.4 ± 10 years, respectively) were included. 57.1% presented hypertension, 16% smoking, 37.6% hypercholesterolemia, 33.8% family history for CAD, and 15.2% DM2. The mean MPR was 2.13 ± 0.48 and 2.21 ± 0.60, mean sMBF was 2.01 ± 0.51 and 2.15 ± 0.54, and mean LVEF was 63% ± 10.4 and 67% ± 10.1 for diabetics and non-diabetics, respectively. A significant relation was detected for sMBF (B = 5.830 95% CI [3.505, 9.549], P = .001) and DM2 (B = −2.599 95% CI [−5.125, −0.119], P = .03) with LVEF. The interaction (DM2 × sMBF) yielded no significance (P = .512). Conclusion: DM2 influences PET-measured systolic function in patients without previous myocardial infarction independently from myocardial perfusion parameters. Our study supports the importance of DM2 as an independent risk factor for deteriorating systolic function.

62 RADIOLOGY AND NUCLEAR MEDICINE↗
DOE OSTI2019

Corrected coronary opacification decrease from coronary computed tomography angiography: Validation with quantitative 13N-ammonia positron emission tomography

Background: To assess the functional relevance of a coronary artery stenosis, corrected coronary opacification (CCO) decrease derived from coronary computed tomography angiography (CCTA) has been proposed. The present study aims at validating CCO decrease with quantitative 13N-ammonia positron emission tomography (PET) myocardial perfusion imaging (MPI). Methods and Results: This retrospective study consists of 39 patients who underwent hybrid CCTA/PET-MPI. From CCTA, attenuation in the coronary lumen was measured before and after a stenosis and corrected to the aorta to calculate CCO and its decrease. Relative flow reserve (RFR) was calculated by dividing the stress myocardial blood flow (MBF) of a vessel territory subtended by a stenotic coronary by the stress MBF of the reference territories without stenoses. RFR was abnormal in 11 vessel territories (27%). CCO decrease yielded a sensitivity, specificity, negative predictive value, positive predictive value, and accuracy for prediction of an abnormal RFR of 73%, 70%, 88%, 47%, and 70%, respectively. Conclusions: CCTA-derived CCO decrease has moderate diagnostic accuracy to predict an abnormal RFR in PET-MPI. However, its high negative predictive value to rule out functional relevance of a given lesion may confer clinical implications in the diagnostic work-up of patients with a coronary stenosis.

62 RADIOLOGY AND NUCLEAR MEDICINE↗
DOE OSTI2024

Microwave-Mediated ammonia synthesis over Co 2 Mo 3 N catalysts at low pressures

The Haber-Bosch process for ammonia (NH 3 ) synthesis is a major contributor to greenhouse gas emissions and is responsible for > 2 % of the world’s energy consumption each year encouraging the need for alternative renewable-based options. Here, this study investigates an earth-abundant ternary metal nitride (i.e., Co 2 Mo 3 N) catalyst to develop a renewable-based NH 3 synthesis approach, utilizing an energy-efficient microwave-assisted route. Using a combination of spectroscopic and catalytic measurements coupled with surface analysis techniques, Co 2 Mo 3 N was evaluated as a stable and efficient NH 3 synthesis catalyst. Results presented here demonstrate NH 3 synthesis on Co 2 Mo 3 N at ~420 °C and ambient pressure yield ~0.7 mmolNH3.g cat -1 .h -1 and up to ~12 mmol NH3 .g cat -1 .h -1 at 28 bar under microwave irradiation. Co 2 Mo 3 N displayed an activation energy of ~72 kJ.mol -1 and yielded NH 3 following first-order kinetics with respect to both H 2 and N 2 . These studies illustrate the potential of using this catalyst for a sustainable, cost-effective, and environmentally friendly approach to producing NH 3 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Elucidating interfacial active sites in ruthenium–boron nitride nanotube catalysts for efficient low-temperature ammonia-to-hydrogen conversion

Tailoring the interaction between metal nanoparticles and catalyst support presents a prominent strategy to enhance both the activity and durability in hydrogen (H 2 ) production catalysts. In this work, ruthenium nanoparticles (NPs) supported on boron nitride nanotubes (Ru/BNNT) are introduced as efficient and thermally robust catalysts for low-temperature ammonia (NH 3 ) decomposition. The unique curvature and ionic nature of BNNTs enable uniform Ru dispersion and metal-support interactions (MSIs), resulting in exceptional H 2 generation efficiency and long-term operational stability. In-situ transmission electron microscopy (TEM) reveals remarkable thermal resistance of Ru/BNNT with minimal nanoparticle sintering, while density functional theory (DFT) calculations uncover a dual-site mechanism in which interfacial Ru atoms promote NH 3 dissociation and adjacent Ru sites facilitate 2H* recombination and H 2 desorption. This cooperative interaction between metal NPs and the BNNT support underpins the outstanding catalytic performance and durability observed. In conclusion, the findings highlight the strategic potential of BNNTs as versatile supports for high-performance and stable catalysts in sustainable H 2 energy conversion and related catalytic processes.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Development, characterization, and modeling of a high-performance Ru/B2CA catalyst for ammonia synthesis

This paper documents the development and performance of a nano-phase Ru catalyst on a (BaO) x (CaO) y (Al 2 O 3 ) support. Extensive screening of the support’s ternary composition shows the best stoichiometry is (BaO) 2 (CaO)(Al 2 O 3 ), denoted B2CA. The paper first describes catalyst preparation and characterization. The paper reports a detailed 12-step reaction mechanism that represents ammonia synthesis over wide ranges of temperature, pressure, space velocity, and feed composition. Additionally, the mechanism is developed and validated using results of packed-bed experiments. The elementary reaction pathways consider surface adsorbates, including catalyst-poisoning behaviors. The rate expressions include important coverage-dependent activation barriers. Machine learning models assist interpretation of the catalyst-support interactions. The detailed chemistry is much more predictive than is possible with global representations (N 2 + 3H 2 ⇌ 2NH 3 ). The validated models can be applied to assist optimizing reactor design and operating conditions.

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

Experimental and numerical investigation of flame stabilization and pollutant formation in matrix stabilized ammonia-hydrogen combustion

Ammonia (NH 3 ) is a carbon-free fuel that offers an attractive alternative for reducing greenhouse gas emissions. However, the slow flame speed, low heating value, and emissions of nitrogen-containing pollutants present significant issues for practical combustion applications. To address these issues, we investigate the use of matrix stabilized combustion. In this type of burner, combustion is performed within an inert porous ceramic foam, heat is recirculated by solid conduction and radiation, which enhances flame speed and combustion stabilization, thereby permitting combustion over a wide range of equivalence ratio conditions. We present a new porous media burner (PMB) capable of stabilizing NH 3 /air flames at ambient conditions. An extensive experimental characterization of the stability of this burner is conducted with up to 30% by volume of hydrogen (H 2 ) in the fuel stream. A 15:1 turndown ratio is demonstrated, with a high thermal power density of 62 MW m -3 . Concentrations of NO, unburnt NH 3 , and H 2 in the exhaust stream are measured. Two regimes are identified for low NO operation: rich and very lean. For rich conditions, NO emissions decrease with increasing equivalence ratio and decreasing H 2 blending. Unburnt NH 3 emissions follow opposite trends. These measurements are complemented by simulations in which the burner is represented by a coupled solid-gas reactor network. In conclusion, this model captures the burner’s pollutant emissions to good accuracy and is used to analyze the mechanisms of pollutant formation.

42 ENGINEERING↗
DOE OSTI2016

Dimension and bridging ligand effects on Mo-mediated catalytic transformation of dinitrogen to ammonia: Chain-like extended models of Nishibayashi’s catalyst

Previous studies suggested that in Nishibayashi’s homogenous catalytic systems based on molybdenum (Mo) complexes, the bimetallic structure facilitated dinitrogen to ammonia conversion in comparison to the corresponding monometallic complexes, likely due to the through-bond interactions between the two Mo centers. However, more detailed model systems are necessary to support this bimetallic hypothesis, and to elucidate the multi-metallic effects on the catalytic mechanism. In this work, we computationally examined the effects of dimension as well as the types of bridging ligands on the catalytic activities of molybdenum-dinitrogen complexes by using a set of extended model systems based on Nishibayashi’s bimetallic structure. The polynuclear chains containing four ([Mo] 4 ) or more Mo centers were found to drastically enhance the catalytic performance by comparing with both the monometallic and bimetallic complexes. Carbide ([:C≡C:] 2– ) was found to be a more effective bridging ligand than N 2 in terms of electronic charges dispersion between metal centers thereby facilitating reactions in the catalytic cycle. Furthermore, the mechanistic modelling suggests that in principle, more efficient catalytic system for N 2 to NH 3 transformation might be obtained by extending the polynuclear chain to a proper size in combination with an effective bridging ligand for charge dispersion.

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

The effects of turbulence on the flame structure and NO formation of ammonia turbulent premixed combustion at various equivalence ratios

Ammonia is carbon-free and is regarded as a potential fuel to address global warming issues. Here, in this work, three-dimensional direct numerical simulations (DNS) of ammonia/air turbulent premixed flames were performed to explore the influence of turbulence and equivalence ratio on the flame structure and NO formation characteristics. Two equivalence ratios were considered, i.e. Φ=0.9 and Φ=1.1. The general flame structures were presented and species distributions were examined. The NO mass fraction was found to be the highest in the product for the lean case and in the reaction zone for the rich case. The conditional mean values of species mass fractions and reaction rates were compared with those of the unstrained and strained laminar premixed flames to explore how well the laminar flame structures can approach those of the turbulent flame. The budget analysis of the species transport equations showed that turbulent diffusion plays an important role in species transport. The turbulent diffusivity D T was estimated using the gradient hypothesis based on the DNS data. Various laminar flame simulations with different diffusivities were carried out. It was shown that the conditional means of the DNS agree well with those of the laminar flames including D T in the transport property calculation. The global and local NO formation characteristics were investigated. It was found that the mean NO production conditioned on the progress variable is lower compared with the corresponding laminar flame in the rich case. However, the relative contributions from various NO pathways are rarely affected by turbulence. The NO mass fraction is higher in negative curvature regions compared with positive curvature regions of the flame surface for the rich case, which is due to the preferential diffusion of H 2 and other radicals and the enhanced NO pathways in negatively curved regions.

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

Simulation of an ammonia-water heat pump water heater with combustion products-driven evaporator

Here, the objective of this work is to simulate a single effct (SE) ammonia-water heat pump for domestic water heating, with innovative aspects for cycle simulation and eventual implementation. Seasonal temperature variations demand verfication of distillation column viability. For the given application and temperature ranges, it is found that some variables need to be controlled if the same column is to be used all year round. In addition, a number of simplifications are considered in this work: an advanced evaporator requireing minimal gas flow and surface area, subcooling at two crucial spots of the cycle and the viability of some pump designs to assuage cavitation issues.

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

Novel geometries for air-cooled condensation of ammonia-water mixtures

An analytical and experimental investigation of air-cooled condensers for small-scale ammonia-water absorption heat pumps is presented. Conventional round-tube corrugated fin design and a novel multi-pass tube array design are considered for a condenser operating at severe ambient conditions within a compact footprint. Segmental heat and mass transfer models are developed to gain a deeper understanding of the characteristics of each design. Predicted heat duties are within 5% of the measured values. The limitations of correlations to predict air-side pressure drop in corrugated fins are identified. The performance of the novel multi-pass tube array condenser was comparable to that of conventional condensers, but is determined to be air-side limited throughout length of the heat exchanger. An improved multi-pass condenser design with fins for increased air-side area is proposed using the insights gained from the modeling and experiments. In closing this design meets the heat duty requirements at severe ambient conditions, while decreasing the size of the heat exchanger by 33%.

42 ENGINEERING↗
DOE OSTI2021

Structure sensitivity of ammonia electro-oxidation on transition metal surfaces: A first-principles study

Ammonia electro-oxidation is a promising catalytic reaction for application in alkaline fuel cells. In this paper we study the trends in this reaction on the (1 0 0) facet of eight fcc transition metals: Au, Ag, Cu, Pt, Pd, Ni, Ir, and Rh. We calculate from first-principles (DFT-GGA-PW91) the energetics for two mechanisms: (i) the N + N mechanism and (ii) the Gerischer-Mauerer mechanism. The onset potentials for both mechanisms are provided for both (1 0 0) and (1 1 1) facets. We also calculate the activation energies for the N-N bond-making non-Faradaic events on Cu, Pt, Pd, Ni, Ir, and Rh. We discover that N* – which is considered a poison for Pt(1 1 1) – is a reactive intermediate on Pt(1 0 0), allowing for a facile dimerization to N2 on Pt(1 0 0) at high potentials. We draw similar analyses for the structure sensitivity on the other metals, and we conclude with some general principles to guide catalyst design for this reaction.

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

Bimetallic NiCo boride nanoparticles confined in a MXene network enable efficient ambient ammonia electrosynthesis

Ambient electrocatalytic nitrogen fixation is an emerging technology for green ammonia synthesis, but the absence of optimized, stable and performant catalysts can render its practical application challenging. Herein, bimetallic NiCo boride nanoparticles confined in MXene are shown to accomplish high-performance nitrogen reduction electrolysis. Taking advantage of the synergistic effect in specific compositions with unique electronic d and p orbits and typical architecture of rich nanosized particles embedded in the interconnected conductive network, the synthesized MXene@NiCoB composite demonstrates extensive improvements in nitrogen molecule chemisorption, active area exposure and charge transport. As a result, optimal NH 3 yield rate of 38.7 μg h -1 mgcat. -1 and Faradaic efficiency of 6.92% are acquired in 0.1 M Na 2 SO 4 electrolyte. Moreover, the great catalytic performance can be almost entirely maintained in the cases of repeatedly-cycled and long-term electrolysis. Theoretical investigations reveal that the nitrogen reduction reaction on MXene@NiCoB catalyst proceeds according to the distal pathway, with a distinctly-reduced energy barrier relative to the Co 2 B counterpart. In conclusion, this work may inspire a new route towards the rational catalyst design for the nitrogen reduction reaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Magnetron sputtered nanostructured cadmium oxide films for ammonia sensing

Nanostructured cadmium oxide (CdO) films were deposited on to glass substrates by reactive dc magnetron sputtering technique. The depositions were carried out for different deposition times in order to obtain films with varying thicknesses. The CdO films were polycrystalline in nature with cubic structure showing preferred orientation in (1 1 1) direction as observed by X-ray diffraction (XRD). Field-emission scanning electron microscope (FE-SEM) micrographs showed uniform distribution of grains of 30–35 nm size and change in morphology from spherical to elliptical structures upon increasing the film thickness. The optical band gap value of the CdO films decreased from 2.67 to 2.36 eV with increase in the thickness. CdO films were deposited on to interdigitated electrodes to be employed as ammonia (NH{sub 3}) gas sensor. The fabricated CdO sensor with thickness of 294 nm has a capacity to detect NH{sub 3} as low as 50 ppm at a relatively low operating temperature of 150 °C with quick response and recovery time. - Highlights: • Nanostructured CdO films were deposited on to glass substrates using magnetron sputtering. • Deposition time was varied in order to obtain films with different thicknesses. • The CdO films were polycrystalline in nature with preferred orientation along (1 1 1) direction. • The optical bandgap values of the films decreased on increasing the thickness of the films. • CdO films with different thickness such as 122, 204, 294 nm was capable to detect NH{sub 3} down to 50 ppm at operating temperature of 150 °C.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗