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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 559 records · Page 31
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

3D printing synthesis of catalysts

The catalyst industry generates approximately $20 billion every year globally and plays a major role in the energy production sector. Traditional industrial catalysts (e.g., pellets) typically have mass and heat transfer limitations, and cause a pressure drop in continuous-flow reactors, lowering the efficiency of the catalytic processes. 3D printing technology has evolved rapidly over the past decade, and the 3D printing of catalysts with desired geometries can address many of the above-stated challenges with traditional catalysts. However, challenges remain to be addressed and opportunities remain to be explored before the full potential in the design and 3D printing of novel catalysts can be realized. Herein this article reviews the recent development in the 3D printing of catalysts. It summarizes the 3D printing design, dimension, property, and performance of 3D printed catalysts. The applications of 3D printed catalysts, such as reforming, wastewater treatment, and CO 2 capture and removal, are discussed, with a techno-economic analysis and life cycle analysis. Future research directions and opportunities for 3D printing of catalysts are also highlighted.

25 ENERGY STORAGE↗
DOE OSTI2022

Electrification and decarbonization of spent Li-ion batteries purification by using an electrochemical membrane reactor

The expanding electric vehicle market brings with it exponential growth in the use of lithium (Li)-ion batteries (LIB) for which a wave of spent LIB is expected to come within the next 5 to 10 years. Due to the economic and strategic value imbedded within the metals contained in LIB, different recycling technologies, including hydrometallurgy, pyrometallurgy and direct recycling, are under development. Being different from previous hydrometallurgical methods, which may have high chemical consumption and negative environmental impact, an electrochemical membrane reactor is designed and validated for the first time, to electrify and decarbonize the impurity removal process. This reactor electroplates copper (Cu) and electrochemically precipitates aluminum (Al) and iron (Fe) from simulated spent LIB leachates, by consuming only air, water, and electricity, and the impurities are reduced to <1 ppm. The purified leachate maintains 99.5 % of the nickel (Ni), 95.4 % of the cobalt (Co) and 99.14 % of manganese (Mn) from the original leachate solution, and then can be directly applied for cathode precursor synthesis. Additionally, the purification process doesn’t introduce extra impurity, and the reactor restoration process generates valuable by-product hydro sulfate (H2SO4). This electrochemical process can reduce the cost, because of the much less chemical consumption and the valuable by-product generation, and mitigates the waste emissions, because of no extra impurity introduced and no greenhouse gas (GHG) produced. In conclusion, the chemical precipitation method uses significant amount of NaOH, which induced GHG emission during the manufacturing process.

25 ENERGY STORAGE↗
DOE OSTI2024

Rational Design of Novel Biomimetic Sequence-Defined Polymers for Mineralization Applications

Silica biomineralization is a naturally occurring process, wherein organisms use proteins and other biological structures to direct the formation of complex, hierarchical nanostructures. Discovery and characterization of such proteins and their underlying mechanisms spurred significant efforts to identify routes for biomimetic mineralization that reproduce the exquisite shapes and size selectivities found in nature. A common strategy has been the use of short peptide sequences with chemistry mimicking those found in natural systems, such as the use of the silaffin-derived R5 peptide. While progress has been made using this approach, there are many limitations that have prevented breakthroughs in biomimicry. To advance our ability to use charged macromolecules for silica formation, we propose to use sequence-defined synthetic polymers known as peptoids, or N-substituted polyglycines, which present significant capability for the precise tuning of sequence and structure beyond what can often be achieved with peptides alone. This study presents a computationally predicted design of these polymers that leads to the controlled formation of silica nanomaterials. We investigate surface adsorption and the mineralization process through analysis of binding mechanisms and energetics of the R5 system. Next, we synthesized two R5-inspired peptoids and validated our prediction in the design of mineralization polymers through characterization using surface plasmon resonance and electron microscopy. Here, this computationally guided study holds great promise for designing new sequences with unprecedented control of the placement of chemical functional groups, thus allowing for further unraveling of silicification mechanisms and the eventual design of sequence-defined synthetic polymers leading to the predictive synthesis of nanostructured functional materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2013

Psychoacoustic Analysis of Synthesized Jet Noise

An aircraft noise synthesis capability is being developed so the annoyance caused by proposed aircraft can be assessed during the design stage. To make synthesized signals as realistic as possible, high fidelity simulation is required for source (e.g., engine noise, airframe noise), propagation and receiver effects. This psychoacoustic study tests whether the jet noise component of synthesized aircraft engine noise can be made more realistic using a low frequency oscillator (LFO) technique to simulate fluctuations in level observed in recordings. Jet noise predictions are commonly made in the frequency domain based on models of time-averaged empirical data. The synthesis process involves conversion of the frequency domain prediction into an audible pressure time history. However, because the predictions are time-invariant, the synthesized sound lacks fluctuations observed in recordings. Such fluctuations are hypothesized to be perceptually important. To introduce time-varying characteristics into jet noise synthesis, a method has been developed that modulates measured or predicted 1/3-octave band levels with a (<20Hz) LFO. The LFO characteristics are determined through analysis of laboratory jet noise recordings. For the aft emission angle, results indicate that signals synthesized using a generic LFO are perceived as more similar to recordings than those using no LFO, and signals synthesized with an angle-specific LFO are more similar to recordings than those synthesized with a generic LFO.

Okcu, Selen↗
DOE OSTI2022

Facile synthesis and phase stability of Cu-based Na 2 Cu(SO 4 ) 2 · x H 2 O ( x = 0–2) sulfate minerals as conversion type battery electrodes

Mineral exploration forms a key approach for unveiling functional battery electrode materials. The synthetic preparation of naturally found minerals and their derivatives can aid in designing of new electrodes. Herein, saranchinaite Na 2 Cu(SO 4 ) 2 and its hydrated derivative kröhnkite Na 2 Cu(SO 4 ) 2 ·2H 2 O bisulfate minerals have been prepared using a facile spray drying route for the first time. The phase stability relation during the (de)hydration process was examined synergising in situ X-ray diffraction and thermochemical studies. Kröhnkite forms the thermodynamically stable phase as the hydration of saranchinaite to kröhnkite is highly exothermic (-51.51 ± 0.63 kJ mol -1 ). Structurally, kröhnkite offers a facile 2D pathway for Na+ ion migration resulting in 20 times higher total conductivity than saranchinaite at 60 °C. Both compounds exhibited a conversion redox mechanism for Li-ion storage with the first discharge capacity exceeding 650 mA h g -1 (at 2 mA g -1 vs. Li + /Li) upon discharge up to 0.05 V. Post-mortem analysis revealed that the presence of metallic Cu in the discharged state is responsible for high irreversibility during galvanostatic cycling. This study reaffirms the exploration of Cu-based polyanionic sulfates, which while having limited (de)insertion properties, can be harnessed for conversion-based electrode materials for batteries.

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

Machine Intelligence-Centered System for Automated Characterization of Functional Materials and Interfaces

Classic design of experiment relies on a time-intensive workflow that requires planning, data interpretation, and hypothesis building by experienced researchers. Here, in this paper, we describe an integrated, machine-intelligent experimental system which enables simultaneous dynamic tests of electrical, optical, gravimetric, and viscoelastic properties of materials under a programmable dynamic environment. Specially designed software controls the experiment and performs on-the-fly extensive data analysis and dynamic modeling, real-time iterative feedback for dynamic control of experimental conditions, and rapid visualization of experimental results. The system operates with minimal human intervention and enables time-efficient characterization of complex dynamic multifunctional environmental responses of materials with simultaneous data processing and analytics. The system provides a viable platform for artificial intelligence (AI)-centered material characterization, which, when coupled with an AI-controlled synthesis system, could lead to accelerated discovery of multifunctional materials.

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

Eliminating dissolution of platinum-based electrocatalysts at the atomic scale

Deployment of proton-exchange membrane fuel cells is limited by the durability of Pt-nanoscale catalysts during cathodic oxygen reduction reactions. Dissolution processes on single crystalline and thin film surfaces are now correlated leading to the design of PtAu catalysts with suppressed dissolution. A remaining challenge for the deployment of proton-exchange membrane fuel cells is the limited durability of platinum (Pt) nanoscale materials that operate at high voltages during the cathodic oxygen reduction reaction. In this work, atomic-scale insight into well-defined single-crystalline, thin-film and nanoscale surfaces exposed Pt dissolution trends that governed the design and synthesis of durable materials. A newly defined metric, intrinsic dissolution, is essential to understanding the correlation between the measured Pt loss, surface structure, size and ratio of Pt nanoparticles in a carbon (C) support. It was found that the utilization of a gold (Au) underlayer promotes ordering of Pt surface atoms towards a (111) structure, whereas Au on the surface selectively protects low-coordinated Pt sites. Finally, this mitigation strategy was applied towards 3 nm Pt 3 Au/C nanoparticles and resulted in the elimination of Pt dissolution in the liquid electrolyte, which included a 30-fold durability improvement versus 3 nm Pt/C over an extended potential range up to 1.2 V.

36 MATERIALS SCIENCE↗
DOE OSTI2022

The Dopamine Assisted Synthesis of MoO3/Carbon Electrodes With Enhanced Capacitance in Aqueous Electrolyte

A capacitance increase phenomenon is observed for MoO 3 electrodes synthesized via a sol-gel process in the presence of dopamine hydrochloride (Dopa HCl) as compared to α-MoO 3 electrodes in 5M ZnCl 2 aqueous electrolyte. The synthesis approach is based on a hydrogen peroxide-initiated sol-gel reaction to which the Dopa HCl is added. The powder precursor (Dopa) x MoO y , is isolated from the metastable gel using freeze-drying. Hydrothermal treatment (HT) of the precursor results in the formation of MoO 3 accompanied by carbonization of the organic molecules; designated as HT-MoO 3 /C. HT of the precipitate formed in the absence of dopamine in the reaction produced α-MoO 3 , which was used as a reference material in this study (α-MoO 3 -ref). Scanning electron microscopy (SEM) images show a nanobelt morphology for both HT-MoO 3 /C and α-MoO 3 -ref powders, but with distinct differences in the shape of the nanobelts. The presence of carbonaceous content in the structure of HT-MoO 3 /C is confirmed by FTIR and Raman spectroscopy measurements. X-ray diffraction (XRD) and Rietveld refinement analysis demonstrate the presence of α-MoO 3 and h-MoO 3 phases in the structure of HT-MoO 3 /C. The increased specific capacitance delivered by the HT-MoO 3 /C electrode as compared to the α-MoO 3 -ref electrode in 5M ZnCl 2 electrolyte in a −0.25–0.70 V vs. Ag/AgCl potential window triggered a more detailed study in an expanded potential window. In the 5M ZnCl 2 electrolyte at a scan rate of 2 mV s −1 , the HT-MoO 3 /C electrode shows a second cycle capacitance of 347.6 F g −1 . The higher electrochemical performance of the HT-MoO 3 /C electrode can be attributed to the presence of carbon in its structure, which can facilitate electron transport. Our study provides a new route for further development of metal oxides for energy storage applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1977

Voice technology and BBN

The following research was discussed: (1) speech signal processing; (2) automatic speech recognition; (3) continuous speech understanding; (4) speaker recognition; (5) speech compression; (6) subjective and objective evaluation of speech communication system; (7) measurement of the intelligibility and quality of speech when degraded by noise or other masking stimuli; (8) speech synthesis; (9) instructional aids for second-language learning and for training of the deaf; and (10) investigation of speech correlates of psychological stress. Experimental psychology, control systems, and human factors engineering, which are often relevant to the proper design and operation of speech systems are described.

Wolf, Jared J.↗
DOE OSTI2020

Role of Capping Agents in the Synthesis of Salicylate-Capped Zinc Oxide Nanoparticles

Capping agents are often used for controlling the size, aggregation, and properties of nanoparticles. To guide the design of improved nanomaterials for targeted performance, one can use mechanistic insights into the interactions between capping agents and nanoparticles. Here, we employ density functional theory (DFT), reactive force-field molecular dynamics (ReaxFF MD) simulations, and optical spectroscopy to study the interactions between salicylate, as a model capping agent, and zinc oxide (ZnO) nanoparticles. In this work, we find that salicylate strongly interacts with the nanoparticle via the formation of O–Zn bonds in a distorted six-membered coordination ring structure. We describe the mechanisms of capping of ZnO nanoparticles by salicylate via three different binding modes. Simulations indicate that salicylate undergoes dissociative adsorption at the highly active surface Zn sites via a hydrogen-transfer process, thereby forming a tridentate configuration. The water-mediated interaction also facilitates the dissociative adsorption, leading to two salicylate O atoms coordinating with a surface Zn atom, while the other salicylate O atom bonds with another surface Zn atom. For molecular adsorption, binding free energies indicate that salicylate binds more strongly to ZnO, often in a bidentate configuration, than water does. The formation of the salicylate–ZnO complex is substantiated by UV–visible and Fourier transform infrared spectra. We find that the C=O stretching mode of salicylate becomes softened when it interacts with the nanoparticle, suggesting chemisorption of salicylate on ZnO. Although DFT predicts strong interaction between salicylate and ZnO, ReaxFF MD simulation indicates the moderate interaction between these two components in aqueous solution. Water molecules in close contact with the nanoparticle surface undergo dissociation, thus resulting in a surface hydroxyl, a reactive oxygen species that may influence the nanoparticle’s catalytic properties. Overall, the atomic-level information provided here can guide the selection process of salicylate as an appropriate agent for ZnO nanoparticle synthesis when strong interactions of particles with capping agents are required.

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

Solid-Binding Proteins: Bridging Synthesis, Assembly, and Function in Hybrid and Hierarchical Materials Fabrication

There is considerable interest in the development of hybrid organic–inorganic materials because of the potential for harvesting the unique capabilities that each system has to offer. Proteins are an especially attractive organic component owing to the high amount of chemical information encoded in their amino acid sequence, their amenability to molecular and computational (re)design, and the many structures and functions they specify. Genetic installation of solid-binding peptides (SBPs) within protein frameworks affords control over the position and orientation of adhesive and morphogenetic segments, and a path toward predictive synthesis and assembly of functional materials and devices, all while harnessing the built-in properties of the host scaffold. Furthermore, we review the current understanding of the mechanisms through which SBPs bind to technologically relevant interfaces, with an emphasis on the variables that influence the process, and highlight the last decade of progress in the use of solid-binding proteins for hybrid and hierarchical materials synthesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1988

A new synthetic route to a family of non-classical addition-type thermoplastics. I - Concept and demonstration

A synthesis scheme was developed for a host of nonclassical addition-type thermoplastics (ATT) that can be cured by an addition reaction, leading to a linear polymer structure. The synthesis involves the reaction of an acetylene-terminated prepolymer with either a bismaleimide (BMI) or a biscitraconimide. A new polymer, designated LaRC-RP80, synthesized using this scheme, was found to exhibit several significantly improved properties over the commercial BMI, Kerimid 601, including an eight-fold increase in toughness while maintaining a high Tg, a higher (by 167 C) heat stability, and a 50-percent increase in moisture resistance. In addition, LaRC-RP80 has good hot/wet lap shear strength and processes easily at 288 C without voids in the finished product.

Pater, Ruth H.↗
DOE OSTI2020

Enhanced and stabilized hydrogen production from methanol by ultrasmall Ni nanoclusters immobilized on defect-rich h-BN nanosheets

Employing liquid organic hydrogen carriers (LOHCs) to transport hydrogen to where it can be utilized relies on methods of efficient chemical dehydrogenation to access this fuel. Therefore, developing effective strategies to optimize the catalytic performance of cheap transition metal-based catalysts in terms of activity and stability for dehydrogenation of LOHCs is a critical challenge. Here, we report the design and synthesis of ultrasmall nickel nanoclusters (∼1.5 nm) deposited on defect-rich boron nitride (BN) nanosheet (Ni/BN) catalysts with higher methanol dehydrogenation activity and selectivity, and greater stability than that of some other transition-metal based catalysts. The interface of the two-dimensional (2D) BN with the metal nanoparticles plays a strong role both in guiding the nucleation and growth of the catalytically active ultrasmall Ni nanoclusters, and further in stabilizing these nanoscale Ni catalysts against poisoning by interactions with the BN substrate. We provide detailed spectroscopy characterizations and density functional theory (DFT) calculations to reveal the origin of the high productivity, high selectivity, and high durability exhibited with the Ni/BN nanocatalyst and elucidate its correlation with nanocluster size and support–nanocluster interactions. This study provides insight into the role that the support material can have both regarding the size control of nanoclusters through immobilization during the nanocluster formation and also during the active catalytic process; this twofold set of insights is significant in advancing the understanding the bottom-up design of high-performance, durable catalytic systems for various catalysis needs.

08 HYDROGEN↗
DOE OSTI2025

Comparing approaches for introducing polycyclic aromatic hydrocarbons to Ge(001) to seed graphene nanoribbon synthesis by CH 4 chemical vapor deposition

Here, we evaluate two approaches for introducing polycyclic aromatic hydrocarbons (PAHs) to a graphene catalyst substrate as part of a two-step chemical vapor deposition (CVD) process for growing graphene nanoribbons (GNRs). In this process, PAHs first form graphene-like seeds on Ge, and then GNRs are subsequently evolved from these PAH-derived seeds via substrate-mediated anisotropic growth kinetics during the CVD of CH4. The first seeding approach sublimes controlled doses of PAH thin films into the CVD chamber, while the second delivers PAHs directly from the vapor phase at set concentrations. Using these two approaches, we measure the dependence of GNR density on PAH dose and compare the experimental results with predictions from a rate model of PAH diffusion, desorption, and clustering. We find that PAHs that more strongly adsorb to the catalyst surface (generally larger PAHs) desirably remain more individualized prior to GNR evolution whereas smaller, more weakly bound PAHs aggregate into larger clusters with various sizes on Ge that are undesirable for synthesizing more monodisperse GNRs. As a result, this work is important because it offers a framework that enables the rational selection and design of seed molecules, advancing anisotropic GNR CVD synthesis.

CVD↗
DOE OSTI2025

Thiol- and Disulfide-Functionalized Polycyclooctene: Metathesis Polymerization, Degradation, and Reformation

The enormous global production and use of polymers and plastics, combined with slower and less efficient disposal and recycling methods, have led to a worldwide growth in plastic waste. Here, we describe an approach that builds degradability into macromolecular polyolefins through the design of telechelic oligomers with reactive functional groups that enables control over polymer deconstruction and reconstruction. Our work exploits disulfide-containing polymers that have emerged as promising cyclable materials due to their dynamic reversibility (bond formation and cleavage) driven by redox chemistry under mild conditions. Specifically, we describe the synthesis of a telechelic α,ω-dithiopolycyclooctene (PCOE) by ring-opening metathesis polymerization using a dithioacetate chain transfer agent, followed by deprotection to convert the chain-end thioacetates to thiols. This process was studied towards control over the degree of oxidation to yield disulfide-containing PCOE, followed by an evaluation of reductive degradation and oxidative repolymerization. Overall, this approach facilitates the production of disulfide-containing unsaturated polyolefins and the integration of degradable and reformable moieties into soluble, processable, metathesis-derived polymers.

Lee, Kyoungwon↗
DOE OSTI2022

Real-time bioelectronic sensing of environmental contaminants

Real-time chemical sensing is crucial for applications in environmental and health monitoring. Biosensors can detect a variety of molecules through genetic circuits that use these chemicals to trigger the synthesis of a coloured protein, thereby producing an optical signal. However, the process of protein expression limits the speed of this sensing to approximately half an hour, and optical signals are often difficult to detect in situ. Here we combine synthetic biology and materials engineering to develop biosensors that produce electrical readouts and have detection times of minutes. Here we programmed Escherichia coli to produce an electrical current in response to specific chemicals using a modular, eight-component, synthetic electron transport chain. As designed, this strain produced current following exposure to thiosulfate, an anion that causes microbial blooms, within 2 min. This amperometric sensor was then modified to detect an endocrine disruptor. The incorporation of a protein switch into the synthetic pathway and encapsulation of the bacteria with conductive nanomaterials enabled the detection of the endocrine disruptor in urban waterway samples within 3 min. Our results provide design rules to sense various chemicals with mass-transport-limited detection times and a new platform for miniature, low-power bioelectronic sensors that safeguard ecological and human health.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Current profile and normalized beta control via feedback linearization and Lyapunov techniques

Abstract Simultaneous control of the current profile and normalized plasma beta is an essential control problem in the development of advanced tokamak scenarios. However, this control problem is especially challenging due to the nonlinear nature of the current, heat, and particle transport dynamics, as well as the difficulty to understand and accurately model such processes. In this work, a nonlinear, robust, model-based controller for the simultaneous regulation of the current profile and normalized beta has been designed using feedback linearization and Lyapunov redesign techniques. Feedback linearization avoids approximate linearization of the plasma dynamics, retaining the original physics content of the model. Moreover, the use of Lyapunov redesign techniques makes the controller robust against the uncertainties arising during the modeling process. The controller’s performance in the presence of unknown dynamics is tested in nonlinear, one-dimensional simulations using the Control Oriented Transport SIMulator (COTSIM) code, which employs plasma models that are significantly more complex than those employed for control synthesis.

Physics↗
DOE OSTI2022

Understanding Photocarrier and Gas Dynamics to Rationally Design Heterostructured Nanocatalysts for Efficient Solar CO 2 Conversion

Recent research in CO 2 photocatalysis has largely focused on exploring new catalysts; however, details of the relationship between charge carrier dynamics and gas dynamics on the surface of nanomaterials often remain unclear. Knowledge of these processes will allow one to rationally design highly efficient catalysts for solar CO 2 conversion. This project aimed to develop state-of-the-art techniques and establish new capabilities in SRNL to enable the study of photocatalysts and other materials in detail. In FY21, we developed two new in situ techniques that are unique to SRNL, allowing the study of reaction intermediates and adsorbed gases during photocatalysis at various wavelengths of excitation. We also established a new in-house capability for catalyst synthesis and product evaluation which enables a deep understanding of how catalyst preparation methodologies impact product generation. In FY22, we gained in-house expertise and knowledge on the newly constructed a physical vapor deposition device, i.e. glancing angle deposition (GLAD) system, and constructed a flow photoreactor system for CO 2 photoconversion and other photocatalytic studies.

79 ASTRONOMY AND ASTROPHYSICS↗