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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 793 records · Page 44
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Mechanistic understanding of catalytic conversion of ethanol to 1-butene over 2D-pillared MFI zeolite

Ethanol is an important C2 platform molecule for producing value-added chemicals and distillate hydrocarbon fuels (e.g., jet and diesel). Among these, catalytic upgrading of ethanol to butenes can generate valuable commodity chemicals (e.g., 1-butene) and provide C4 olefin intermediates that can be further upgraded to jet/diesel fuels. 2D zeolites offer hierarchical mesoporous structures, leading to improved mass transport and reduced diffusion length, which can help to address the coking challenges faced by ethanol conversion to hydrocarbons over 3D zeolites. In this study, we investigate the acid-catalyzed conversion of ethanol to 1-butene over the Brønsted acid sites (BAS) in 2D-pillared MFI zeolite (2D-PMFI) using ab initio molecular dynamics (AIMD) simulations, in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and calorimetric measurements. A detailed thermodynamic analysis, using quasi-harmonic approximation (QHA), on the Gibbs free energy pathway of ethanol conversion shows that the consideration of entropy is critical to accurately capture the detailed thermodynamic profiles. The formation of bulky ethoxy-ethene complex is found to be a potential rate-determining step (RDS), proceeding via stepwise mechanism. The reactivity of 2D-PMFI can be further tuned by manipulating RDS through a careful control of number of BAS and operating temperatures. The accuracy of computational model is confirmed through the comparison of calculated vibrational density of states (VDOS) against the experimental DRIFTS measurements. Overall, our study provides mechanistic insights into ethanol upgrading over the 2D-PMFI and shows the importance of evaluating entropic effects in such confined system.

Ethanol conversion, 2D-pillared zeolite, MFI, Anha↗
DOE OSTI2022

Methods for microwave characterization of electro-optic crystals for quantum transduction

Microwave-optic quantum transducers are essential devices to develop distributed quantum networks and implement related quantum communication protocols. Three dimensional high-coherence time microwave cavities embedded with electro-optic nonlinear dielectric materials provide promising platforms to boost the efficiency of the microwave-optic frequency conversion. However, so far, the properties for such dielectric crystals operating at milli-Kelvin cryogenic temperatures have not been well understood. Here, we propose a scheme to precisely measure and benchmark the dielectric constant and analyze the dissipation mechanisms of electro-optic materials, such as Lithium Niobate, at the quantum threshold. We will use Fermilab’s three dimensional superconducting cavities with long coherence time. The proposed method of microwave characterization lays the foundations for engineering quantum transduction devices and quantum sensors with high conversion efficiency and fidelity.

Zorzetti, Silvia↗
DOE OSTI2023

Precise synthesis and photovoltaic properties of giant molecule acceptors

Series of giant molecule acceptors DY, TY and QY with two, three and four small molecule acceptor subunits are synthesized by a stepwise synthetic method and used for systematically investigating the influence of subunit numbers on the structure-property relationship from small molecule acceptor YDT to giant molecule acceptors and to polymerized small molecule acceptor PY-IT. Among these acceptors-based devices, the TY-based film shows proper donor/acceptor phase separation, higher charge transfer state yield and longer charge transfer state lifetime. Combining with the highest electron mobility, more efficient exciton dissociation and lower charge carrier recombination properties, the TY-based device exhibits the highest power conversion efficiency of 16.32%. These results indicate that the subunit number in these acceptors has significant influence on their photovoltaic properties. This stepwise synthetic method of giant molecule acceptors will be beneficial to diversify their structures and promote their applications in high-efficiency and stable organic solar cells.

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

Sensor Distortion Effects in Photon Monte Carlo Simulations

We present a detailed method to simulating sensor distortions using a photon and electron Monte Carlo method. We use three-dimensional electrostatic simulations to parameterize the perturbed electric field profile for nonideal sensor details. We follow the conversion of simulated photons, and the subsequent response of the converted electrons to the electric field pattern. These nonideal sensor details can be implemented efficiently in a Monte Carlo approach. We demonstrate that the nonideal sensor distortions have a variety of observable consequence including the modification of the astrometric pattern; the distortion of the electron diffusion size and shape; and the distortion of flats. We show analytic validation of the diffusion physics, reproduce two kinds of edge distortion, and show qualitative validation of field-free regions, lithography errors, and fringing. We also demonstrate that there are two related effects of doping variation having different observable consequences. We show that field distortions from accumulated electrons lead to intensity-dependent point-spread functions and the sublinear variance in flats. The method is implemented in the Photon Simulator and the code is publicly available.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2024

Rapid measurement of soluble xylo-oligomers using near-infrared spectroscopy (NIRS) and multivariate statistics: calibration model development and practical approaches to model optimization

Rapid monitoring of biomass conversion processes using techniques such as near-infrared (NIR) spectroscopy can be substantially quicker and less labor-, resource-, and energy-intensive than conventional measurement techniques such as gas or liquid chromatography (GC or LC) due to the lack of solvents and preparation methods, as well as removing the need to transfer samples to an external lab for analytical evaluation. The purpose of this study was to determine the feasibility of rapid monitoring of a biomass conversion process using NIR spectroscopy combined with multivariate statistical modeling, and to examine the impact of (1) subsetting the samples in the original dataset by process location and (2) reducing the spectral range used in the calibration model on model performance. We develop multivariate calibration models for the concentrations of soluble xylo-oligosaccharides (XOS), monomeric xylose, and total solids at multiple points in a biomass conversion process which produces and then purifies XOS compounds from sugar cane bagasse. A single model using samples from multiple locations in the process stream showed acceptable performance as measured by standard statistical measures. However, compared to the single model, we show that separate models built by segregating the calibration samples according to process location show improved performance. We also show that combining an understanding of the sample spectra with simple multivariate analysis tools can result in a calibration model with a substantially smaller spectral range that provides essentially equal performance to the full-range model. We demonstrate that real-time monitoring of soluble xylo-oligosaccharides (XOS), monomeric xylose, and total solids concentration at multiple points in a process stream using NIR spectroscopy coupled with multivariate statistics is feasible. Segregation of sample populations by process location improves model performance. Models using a reduced spectral range containing the most relevant spectral signatures show very similar performance to the full-range model, reinforcing the importance of performing robust exploratory data analysis before beginning multivariate modeling.

09 BIOMASS FUELS↗
DOE OSTI2024

A data-driven method to constrain the $\bar{p}$ background in Mu2e

The Mu2e experiment will search for the charged lepton flavour violating process of neutrinoless coherent muon to electron conversion in the field of an Al nucleus. The expected signal is a 104.97 MeV/c electron. One of the expected backgrounds is due to ¯ps produced by the proton beam at the Production Target and annihilating in the Stopping Target (ST). The background from ¯p annihilation is not a dominant one, but it has a large uncertainty and it cannot be suppressed by the timing cuts used to reduce the prompt background. However at Mu2e energies, p¯p annihilation is the only source of events with multiple simultaneous tracks coming from the ST. We exploit this unique feature and reconstruct the multi-track events to estimate the ¯p background.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2022

PdCu Electrocatalysts for Selective Nitrate and Nitrite Reduction to Nitrogen

Electrocatalytic conversion of nitrate in waste can enable efficient waste remediation (NO 3 - to N 2 ) or waste valorization (NO 3 - to NH 4 + ) depending on the selectivity of the catalyst. Palladium and copper electrocatalysts typically exhibit ideal nitrate and nitrite binding properties, allowing for effective destruction of nitrate. However, rational steering of selectivity through material design remains a critical challenge for PdCu electrocatalyst. Here, we use the electrochemical underpotential deposition method to synthesize palladium nanocube electrocataysts with controlled copper surface coverage (e.g., partial and full copper coatings). We then examine the potential for NO 3 - destruction (conversion) and NO 2 - reduction reaction. We identify that partial copper-coated Pd nanocubes not only effectively facilitate the reduction of 95% of NO 3 - but also increase the reduction of NO 2 - to N 2 with 89% selectivity over 20 consecutive cycles (80 h). We also show that under these conditions, the Pd(100) surface facet is exposed. Complete copper-covered Pd nanocubes effectively facilitate the reduction of ~99% of NO 3 - . Complete coverage of copper; however, prevented exposure of Pd(100) surface facet, promoting the selective reduction of NO 2 - to NH 4 + with a 70% selectivity over 20 consecutive cycles (80 h). Density functional theory (DFT) calculations show that NO 3 - and NO 2 - adsorb more strongly on the Cu(100) surface compared to the Pd(100) surface, while the NO* intermediate generated from NO 3 - or NO 2 - reduction adsorbs more strongly on the Pd surface. Furthermore, barrier calculations show that NO* can readily migrate from the Cu domain to the Pd domain and that the N–N coupling barrier on Pd is significantly diminished at high NO* coverage. Together, these results suggest that the high N 2 selectivity observed on the PdCu electrocatalyst is caused by the spillover of NO* from the Cu domains to the Pd domains.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Aggregation‐Induced Multilength Scaled Morphology Enabling 11.76% Efficiency in All‐Polymer Solar Cells Using Printing Fabrication

Abstract All‐polymer solar cells (all‐PSCs) exhibit excellent stability and readily tunable ink viscosity, and are therefore especially suitable for printing preparation of large‐scale devices. At present, the efficiency of state‐of‐the‐art all‐PSCs fabricated by the spin‐coating method has exceeded 11%, laying the foundation for the preparation and practical utilization of printed devices. A high power conversion efficiency (PCE) of 11.76% is achieved based on PTzBI‐Si:N2200 all‐PSCs processing with 2‐methyltetrahydrofuran (MTHF, an environmentally friendly solvent) and preparation of active layers by slot die printing, which is the top efficient for all‐PSCs. Conversely, the PCE of devices processed by high‐boiling point chlorobenzene is less than 2%. Through the study of film formation kinetics, volatile solvents can freeze the morphology in a short time, and a more rigid conformation with strong intermolecular interaction combined with the solubility limit of PTzBI‐Si and N2200 in MTHF results in the formation of a fibril network in the bulk heterojunction. The multilength scaled morphology ensures fast transfer of carriers and facilitates exciton separation, which boosts carrier mobility and current density, thus improving the device performance. These results are of great significance for large‐scale printing fabrication of high‐efficiency all‐PSCs in the future.

Zhu, Lei↗
DOE OSTI2016

Understanding the interactions of CO 2 with doped and undoped SrTiO 3

SrTiO 3 and doped SrTiO 3 have a wide range of applications in different fields. For example, Rh-doped SrTiO 3 has been shown to have photocatalytic activity for both hydrogen production and CO 2 conversion. In this study, both undoped and Rh-doped SrTiO 3 were synthesized by hydrothermal and polymerizable complex methods. Different characterizations techniques including X-ray photoelectron spectroscopy (XPS), XRD, Raman, and UV/Vis spectroscopy were utilized to establish correlations between the preparation methods and the electronic/structural properties of Rh-doped SrTiO 3 . The presence of dopants and oxygen vacancies substantially influenced the CO 2 interactions with the surface, as revealed by the in situ infrared spectroscopic study. As a result, the presence of distinctly different adsorption sites was correlated to oxygen vacancies and oxidation states of Ti and Rh.

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

Outstanding Platinum Group Metal-free Bifunctional Catalysts for Rechargeable Zinc-Air Batteries

Developing highly active and durable catalysts for zinc-air batteries (ZAB) is critical for energy conversion and storage. Herein, we prepared Fe-N-C catalysts at a kilogram scale by the commercial VariPore™ method and the effect of synthesis conditions on the catalyst performance at ZAB air electrode was investigated. The results show the PA-450-HT exhibits excellent electrocatalytic activity toward oxygen reduction reaction (ORR) and it is the most suitable catalyst for primary ZAB with the galvanostatic polarization discharge peak power density of 149 mW cm -2 , outperforming commercial Pt-Ru/C catalysts. Additionally, the NCB-600-HT catalyst displays the half-wave potential of 0.87 V vs. RHE for ORR and ΔE value of 0.81 V (indicating outstanding ORR and OER reversibility) and exhibits excellent charge-discharge cycling durability similar to NCB-550-LT around 160 h for the secondary ZAB. This work reports outstanding bifunctional Fe-N-C catalysts for rechargeable ZAB at mass production for the first time.

25 ENERGY STORAGE↗
DOE OSTI2018

Quinone-mediated electrochemical O2 reduction accessing high power density with an off-electrode heterogeneous catalyst

New methods for interconversion of electrical and chemical energy are crucial to address emerging challenges in renewable energy storage and conversion. Dissolved redox mediators provide an effective means to transport electrons (and protons) between an electrode and catalysts that are not in direct physical contact with an electrode. Mediators are widely implemented in biofuel cells, but such devices typically exhibit low power densities. Here, we report the development of a tetrasubstituted quinone mediator that exhibits excellent stability under strongly acidic conditions and supports electrochemical reduction of O2 at an off-electrode heterogeneous cobalt catalyst contained within a packed-bed reactor. Efficient oxidation of the hydroquinone by O2 in the reactor provides the basis for mediator regeneration, and an integrated “flow cathode” system supports high fuel-cell power densities. These results establish the combination of organic mediators with off-electrode heterogeneous catalysts as a versatile platform for development of new electrode-driven chemical redox transformations.

Preger, Yuliya↗
DOE OSTI2020

In-situ and in-operando analysis of voltage losses using sense wires for proton exchange membrane water electrolyzers

Proton exchange membrane water electrolyzer development requires understanding processes at the materials and interface levels to reach the required performance and lifetime targets for increasing market penetration. To achieve the required progress, it is critical to develop advanced in-situ diagnostics that allow observation of the changes that come with the reduction of catalyst loading combined with long-term intermittent operation. This work presents an internal voltage sensing method that enables observing internal voltage drops in an operating electrolyzer cell. It allows the total cell resistance to be separated into anode, CCM, and cathode resistance. The method is demonstrated by operating cells with different anode porous transport layers (PTLs). The changing properties of the PTLs result in significant variations of the resistances. Enhancing the PTL properties with a protective coating reduces the anode resistance significantly. In addition to these observations, the method enables a real-time monitoring of resistance related values that impact performance in water electrolyzers. Long-term experiments with the method allow us to gain insights into processes that occur during operation such as conditioning or degradation. The internal voltage sensing method presented in this study is a novel technique for diagnosing, analyzing, and optimizing water electrolyzers and other energy conversion devices.

42 ENGINEERING↗
DOE OSTI2015

NaLa(MoO{sub 4}){sub 2}: RE{sup 3+} (RE{sup 3+} = Eu{sup 3+}, Sm{sup 3+}, Er{sup 3+}/Yb{sup 3+}) microspheres: the synthesis and optical properties

The strong green upconversion (UC) emission were observed in various Er{sup 3+}, Yb{sup 3+} co-doped NaLa(MoO{sub 4}){sub 2} samples synthesized via a hydrothermal route. The UC intensity depends on the dopant concentration, and the optimal UC emission was obtained in NaLa(MoO{sub 4}){sub 2}: 0.02Er{sup 3+}/0.10 Yb{sup 3+}. - Highlights: • The NaLa(MoO{sub 4}){sub 2} microspheres doped with Eu{sup 3+}, Sm{sup 3+} and Er{sup 3+}/Yb{sup 3+} were synthesized by a hydrothermal method. • The effects of the EDTA in the initial solution crystal phase and morphology were studied. • The down-conversion luminescence properties of NaLa(MoO{sub 4}){sub 2}: RE{sup 3+} (RE{sup 3+} = Eu{sup 3+}, Sm{sup 3+}) were investigated. • The UC luminescence properties and mechanism of Er{sup 3+}/Yb{sup 3+} co-doped NaLa(MoO{sub 4}){sub 2} was discussed. - Abstract: NaLa(MoO{sub 4}){sub 2}: RE{sup 3+} (RE{sup 3+} = Eu{sup 3+}, Sm{sup 3+}) microspheres have been synthesized at 180 °C via a facile EDTA-mediated hydrothermal route. X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), photoluminescence (PL) spectra were employed to characterize the samples. It was found that the amount of EDTA in the initial solution was responsible for crystal phase and shape determination. The effect of Eu{sup 3+} and Sm{sup 3+} doping concentrations on the luminescent intensity was also investigated in details. Furthermore, the up-conversion (UC) emissions have been observed in a series of Er{sup 3+}/Yb{sup 3+} co-doped NaLa(MoO{sub 4}){sub 2} samples. Concentration dependent studies revealed that the optimal composition was realized for a 2% Er{sup 3+} and 10% Yb{sup 3+}-doping concentration.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Synthetic Chlorins, Possible Surrogates for Chlorophylls, Prepared by Derivatization of Porphyrins

Chlorophylls make Earth green, are the central constituents in the engine of photosynthesis, and not surprisingly have garnered extensive attention. A chlorin, the core chromophore of a chlorophyll, is a dihydroporphyrin macrocycle that contains one pyrroline ring and three pyrrole rings. The dominant method for the synthesis of chlorins has entailed the derivatization of porphyrins. The present review covers the ostensibly simple conversion of porphyrins, regardless of synthetic or biological origin, to chlorins. The period covered encompasses the entire history since the beginnings of chlorin synthetic chemistry in the early 20th century through 2015. Representative transformations include hydrogenation, cycloaddition, annulation, and diverse “breaking and mending” approaches. Altogether, the synthesis of >1000 chlorins or chlorin-like compounds (containing >50 distinct pyrroline motifs) is described. Such diversity animates the question “what structural features are essential for a chlorin to resemble chlorophyll?” To begin to address the structure–spectrum relationship, > 250 absorption spectra are provided for representative structures. The synthesis and spectral properties of the vast collection of compounds described herein are expected to illuminate the scope to which synthetic chlorins can serve as surrogates for chlorophylls and be exploited in diverse ways.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Determining the Reaction Kinetics and Thermodynamics of a Diels–Alder Network Using Dynamic Gel Criteria

We undertook a detailed rheological investigation to evaluate the kinetic parameters of the forward and reverse Diels–Alder (DA) reactions of a model network cross-linked using a furan prepolymer and a common aromatic bismaleimide. At high temperature where the Winter–Chambon’s criterion of frequency-independence was more applicable, a multiwave technique permitted van’t Hoff analysis and calculation of the reaction thermodynamic parameters, specifically the enthalpy and entropy of the reaction: ΔH° = –38.3 ± 5.2 kJ mol –1 and ΔS° = –94.3 ± 13.4 J mol –1 . At mild temperatures where the G'–G" crossover point is experimentally convenient to measure gelation, isothermal tests were used to obtain reasonable fDA kinetic parameters from Eyring analysis such as the apparent activation enthalpy and entropy of ΔH$^{‡}_{fDA}$ = 76.8 ± 6.9 kJ mol –1 and ΔS$^{‡}_{fDA}$= –82.8 ± 22.2 J mol –1 K –1 . Comparable rheokinetic methods include cross-linking density measurements and stress relaxation tests to calculate effective kinetics, whereas the critical gel conversion was consistently applied here. As a result, rate data are fitted with the Arrhenius equation for comparison purposes and the Eyring equation to demonstrate its broader utility.

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

Electrochemically Engineered, Highly Energy-Efficient Conversion of Ethane to Ethylene and Hydrogen below 550 °C in a Protonic Ceramic Electrochemical Cell

Ethylene is one of the largest building blocks in the petrochemical industry, mainly produced by steam cracking of ethane derived from naphtha or shale gas at high temperatures (>800 °C). Despite its technical maturity and economic competitiveness, the thermal steam cracking of ethane is highly energy-intensive. In this work, an electrochemically engineered direct conversion process of ethane to produce hydrogen and ethylene using a planar protonic ceramic membrane reactor with a bi-functional three-dimensional catalytic electrode is reported, with a single-pass ethane conversion of 40% and ethylene yield of 26.7% at 550 °C. Compared with the industrial ethane steam cracking, this method saves process energy input by 45.1% and improves process energy efficiency by 50.6%, based on comprehensive process simulation using Aspen Plus software. Further, steam electrolysis treatment under the solid oxide electrolysis cell mode can regenerate the system’s catalytic performance and significantly alleviate catalytic degradation by 74%, demonstrating high techno-economic viability.

bi-functional electrode↗
DOE OSTI2017

Ru-Sn/AC for the Aqueous-Phase Reduction of Succinic Acid to 1,4-Butanediol under Continuous Process Conditions

Succinic acid is a biomass-derived platform chemical that can be catalytically converted in the aqueous phase to 1,4-butanediol (BDO), a prevalent building block used in the polymer and chemical industries. Despite significant interest, limited work has been reported regarding sustained catalyst performance and stability under continuous aqueous-phase process conditions. As such, this work examines Ru-Sn on activated carbon (AC) for the aqueous-phase conversion of succinic acid to BDO under batch and flow reactor conditions. Initially, powder Ru-Sn catalysts were screened to determine the most effective bimetallic ratio and provide a comparison to other monometallic (Pd, Pt, Ru) and bimetallic (Pt-Sn, Pd-Re) catalysts. Batch reactor tests determined that a ~1:1 metal weight ratio of Ru to Sn was effective for producing BDO in high yields, with complete conversion resulting in 82% molar yield. Characterization of the fresh Ru-Sn catalyst suggests that the sequential loading method results in Ru sites that are colocated and surface-enriched with Sn. Postbatch reaction characterization confirmed stable Ru-Sn material properties; however, upon a transition to continuous conditions, significant Ru-Sn/AC deactivation occurred due to stainless steel leaching of Ni that resulted in Ru-Sn metal crystallite restructuring to form discrete Ni-Sn sites. Computational modeling confirmed favorable energetics for Ru-Sn segregation and Ni-Sn formation at submonolayer Sn incorporation. To address stainless steel leaching, reactor walls were treated with an inert silica coating by chemical vapor deposition. With leaching reduced, stable Ru-Sn/AC performance was observed that resulted in a molar yield of 71% BDO and 15% tetrahydrofuran for 96 h of time on stream. Postreaction catalyst characterization confirmed low levels of Ni and Cr deposition, although early-stage islanding of Ni-Sn will likely be problematic for industrially relevant time scales (i.e., thousands of hours). Overall, these results (i) demonstrate the performance of Ru-Sn/AC for aqueous phase succinic acid reduction, (ii) provide insight into the Ru-Sn bimetallic structure and deactivation in the presence of leached Ni, and (iii) underscore the importance of compatible reactor metallurgy and durable catalysts.

09 BIOMASS FUELS↗
DOE OSTI2020

Voltage bias stress effects in metal halide perovskites are strongly dependent on morphology and ion migration pathways

The solar-to-power power conversion efficiencies (PCEs) of metal halide perovskites (MHP) have improved over the last decade using a wide variety of methods, including composition manipulation, dopant introduction, and interfacial buffers. These methods, however, have taken little regard for the electronic and interfacial effects such alterations may cause within devices under voltage bias stress – a condition required for most device operation. We investigate how halide and cation substitution in MHP structures [specifically, CH 3 NH 3 PbI 2.87 Cl 0.13 and Cs 0.1 (MA 0.17 FA 0.83 ) 0.9 Pb(I 0.83 Br 0.17 ) 3 ] effects the current behavior of devices while under a range of voltage bias stress in both light and dark conditions. Additionally, conducting in depth investigations into the electronic and morphological differences between these two MHP devices, we confirmed their unique voltage bias stress effects are due to intrinsic behavior within the perovskite structure. Importantly, we also determined how crystallite orientation can influence ion migration and therefore alter charge transport and current stability in MHP photovoltaic devices.

36 MATERIALS SCIENCE↗