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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 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Silica–Derived Nanostructured Electrode Materials for ORR, OER, HER, CO 2 RR Electrocatalysis, and Energy Storage Applications: A Review**

Silica-derived nanostructured catalysts (SDNCs) are a class of materials synthesized using nanocasting and templating techniques, which involve the sacrificial removal of a silica template to generate highly porous nanostructured materials. The surface of these nanostructures is functionalized with a variety of electrocatalytically active metal and non-metal atoms. SDNCs have attracted considerable attention due to their unique physicochemical properties, tunable electronic configuration, and microstructure. These properties make them highly efficient catalysts and promising electrode materials for next generation electrocatalysis, energy conversion, and energy storage technologies. The continued development of SDNCs is likely to lead to new and improved electrocatalysts and electrode materials. This review article provides a comprehensive overview of the recent advances in the development of SDNCs for electrocatalysis and energy storage applications. It analyzes 337,061 research articles published in the Web of Science (WoS) database up to December 2022 using the keywords “silica”, “electrocatalysts”, “ORR”, “OER”, “HER”, “HOR”, “CO 2 RR”, “batteries”, and “supercapacitors”. The review discusses the application of SDNCs for oxygen reduction reaction (ORR), oxygen evolution reaction (OER), hydrogen evolution reaction (HER), carbon dioxide reduction reaction (CO 2 RR), supercapacitors, lithium-ion batteries, and thermal energy storage applications. It concludes by discussing the advantages and limitations of SDNCs for energy applications.

25 ENERGY STORAGE↗
DOE OSTI2020

Highly Tunable Thiol-Ene Photoresins for Volumetric Additive Manufacturing

Volumetric additive manufacturing (VAM) forms complete 3D objects in a single photocuring operation without layering defects, enabling 3D printed polymer parts with mechanical properties similar to their bulk material counterparts. This study presents the first report of VAM-printed thiol-ene resins. With well-ordered molecular networks, thiol-ene chemistry accesses polymer materials with a wide range of mechanical properties, moving VAM beyond the limitations of commonly used acrylate formulations. Since free-radical thiol-ene polymerization is not inhibited by oxygen, the nonlinear threshold response required in VAM is introduced by incorporating 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) as a radical scavenger. Tuning of the reaction kinetics is accomplished by balancing inhibitor and initiator content. Coupling this with quantitative measurements of the absorbed volumetric optical dose allows control of polymer conversion and gelation during printing. Importantly, this work thereby establishes the first comprehensive framework for spatial–temporal control over volumetric energy distribution, demonstrating structures 3D printed in thiol-ene resin by means of tomographic volumetric VAM. Mechanical characterization of this thiol-ene system, with varied ratios of isocyanurate and triethylene glycol monomers, reveals highly tunable mechanical response far more versatile than identical acrylate-based resins. This broadens the range of materials and properties available for VAM, taking another step toward high-performance printed polymers.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Tailored ultrasound propagation in microscale metamaterials via inertia design

The quasi-static properties of micro-architected (meta)materials have been extensively studied over the past decade, but their dynamic responses, especially in acoustic metamaterials with engineered wave propagation behavior, represent a new frontier. However, challenges in miniaturizing and characterizing acoustic metamaterials in high-frequency (megahertz) regimes have hindered progress toward experimentally implementing ultrasonic-wave control. Here, we present an inertia design framework based on positioning microspheres to tune responses of 3D microscale metamaterials. We demonstrate tunable quasi-static stiffness by up to 75% and dynamic longitudinal-wave velocities by up to 25% while maintaining identical material density. Using noncontact laser-based dynamic experiments of tunable elastodynamic properties and numerical demonstrations of spatio-temporal ultrasound wave propagation, we explore the tunable static and elastodynamic property relation. This design framework expands the quasi-static and dynamic metamaterial property space through simple geometric changes, enabling facile design and fabrication of metamaterials for applications in medical ultrasound and analog computing.

42 ENGINEERING↗
DOE OSTI2024

Inter-Oligomer Interaction Influence on Photoluminescence in Cis-Polyacetylene Semiconductor Materials

Semiconducting conjugated polymers (CPs) are pivotal in advancing organic electronics, offering tunable properties for solar cells and field-effect transistors. Here, we carry out first-principle calculations to study individual cis-polyacetylene (cis-PA) oligomers and their ensembles. The ground electronic structures are obtained using density functional theory (DFT), and excited state dynamics are explored by computing nonadiabatic couplings (NACs) between electronic and nuclear degrees of freedom. We compute the nonradiative relaxation of charge carriers and photoluminescence (PL) using the Redfield theory. Our findings show that electrons relax faster than holes. The ensemble of oligomers shows faster relaxation compared to the single oligomer. The calculated PL spectra show features from both interband and intraband transitions. The ensemble shows broader line widths, redshift of transition energies, and lower intensities compared to the single oligomer. This comparative study suggests that the dispersion forces and orbital hybridizations between chains are the leading contributors to the variation in PL. It provides insights into the fundamental behaviors of CPs and the molecular-level understanding for the design of more efficient optoelectronic devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Substitutional doping of 2D transition metal dichalcogenides for device applications: Current status, challenges and prospects

Two-dimensional (2D) transition metal dichalcogenides (TMDs) have emerged as a class of materials with exceptional electronic, optical, and mechanical properties, making them highly tunable for diverse applications in nanoelectronics, optoelectronics, and catalysis. Here, this review focuses on substitutional doping of TMDs, a key strategy to tailor their properties and enhance device performance, with a focus on its applications over the past five years (2019–2024). We delve into both theoretical and experimental doping approaches, including established methods like chemical vapor transport (CVT) and chemical vapor deposition (CVD) alongside liquid phase exfoliation (LPE) and post-synthesis treatments. Advanced growth techniques are also explored. Challenges like dopant uniformity, concentration control, and stability are addressed. The influence of various dopants on the electronic band structure, carrier concentration, and defect engineering is analyzed in detail. We further explore recent advancements in utilizing doped TMDs for field-effect transistors (FETs), photodetectors, sensors, photovoltaics, optoelectronic devices, energy storage and conversion, and even quantum computers. By examining both the potential and limitations of substitutional doping, this review aims to propel future research and technological advancements in this exciting field.

36 MATERIALS SCIENCE↗
DOE OSTI2021

2D Covalent Organic Frameworks with an Incorporated Manganese Complex for Light Driven Carbon Dioxide Reduction

Covalent organic frameworks (COFs) have emerged as a novel class of crystalline porous photocatalytic materials due to their unique properties such as large surface area, tunable porosity, and rigid structure. Here in this work, we report the direct incorporation of a manganese CO 2 molecular catalyst (MC) into COFs (Mn-TTA-COF) and the evaluation of its capability as photocatalyst for visible light driven CO 2 reduction to form CO. We found that the photocatalytic activity of Mn-TTA-COF is quite low, which mainly results from the elimination of the CO ligand in the Mn MC upon light illumination, rendering its short duration in the catalytic reaction. While this is a central concern for the further use Mn-TTA-COF as a CO 2 reduction catalyst, here we found that the stability and efficiency of Mn MC is largely enhanced after being incorporated into COFs with respect to its homogeneous version, suggesting the capability of COFs as heterogeneous platform to incorporate MC and improve the catalytic performance of MC. Moreover, transient absorption spectroscopic studies show that the intramolecular charge transfer lifetime of the Mn-incorporated COF is longer than that in the parent COF, which suggests that charge separation (CS) may occur from the parent COF to the Mn moiety. These results together suggest that COFs may show promise as a platform for creating next-generation photocatalysts with a built-in photosensitizer and MC, which can facilitate CS and enhance the stability and efficiency of the incorporated MC.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Elucidating the Interfacial Effects of Nonmetallic Elements on the Dehydrogenation Behavior of Nanoconfined NaAlH 4 in Zeolite-Templated Carbon

Confining materials within nanoscale volumes alters their physical and chemical properties, with positive consequences for energy storage, conversion, and catalysis. The pore structure and composition of scaffolds are essential variables for optimizing these properties, with carbon-based materials being preferred due to their tunable porous structures and chemical versatility. This study investigates the influence of surface functional groups on the dehydrogenation kinetics of nanoconfined NaAlH4 using zeolite-templated carbons (ZTCs). Here we focus on oxygen functional groups commonly present as intrinsic impurities on carbon scaffolds, analyzing three ZTC scaffolds to determine how their concentrations and configurations affect dehydrogenation behavior. Our findings reveal that carbonyl groups enhance charge transfer and destabilize Al–H bonds more effectively than ether or phenol groups. This indicates that the type of oxygen functional group is more critical than the quantity, highlighting the importance of properly tailoring oxygen defects to improve hydrogen storage performance in nanoconfined systems.

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

Understanding capacity fade in organic redox-flow batteries by combining spectroscopy with statistical inference techniques

Organic redox-active molecules are attractive as redox-flow battery (RFB) reactants because of their low anticipated costs and widely tunable properties. Unfortunately, many lab-scale flow cells experience rapid material degradation (from chemical and electrochemical decay mechanisms) and capacity fade during cycling (>0.1%/day) hindering their commercial deployment. In this work, we combine ultraviolet-visible spectrophotometry and statistical inference techniques to elucidate the Michael attack decay mechanism for 4,5-dihydroxy-1,3-benzenedisulfonic acid (BQDS), a once-promising positive electrolyte reactant for aqueous organic redox-flow batteries. We use Bayesian inference and multivariate curve resolution on the spectroscopic data to derive uncertainty-quantified reaction orders and rates for Michael attack, estimate the spectra of intermediate species and establish a quantitative connection between molecular decay and capacity fade. Our work illustrates the promise of using statistical inference to elucidate chemical and electrochemical mechanisms of capacity fade in organic redox-flow battery together with uncertainty quantification, in flow cell-based electrochemical systems.

25 ENERGY STORAGE↗
DOE OSTI2021

Tuning the critical Li intercalation concentrations for MoX 2 (X = S, Se, or Te) bilayer phase transitions

Transition metal dichalcogenides (TMDs), such as MoS 2 , are known to undergo a structural phase transformation as well as a change in the electronic conductivity upon Li intercalation. These properties make them candidates for charge-tunable ion-insertion materials that could be used in electro-chemical devices. In this work we study the phase stability and electronic structure of H and T’ Li-intercalated MoX 2 bilayers with X=S, Se, or Te. Here, using first-principles calculations in combination with classical and machine learning modeling approaches, we find that the H phase is more stable at low Li concentration for all X, and the critical Li concentration at which the T’→H transition occurs decreases with increasing mass of X. Furthermore the relative free energy of the two phases becomes less sensitive to Li insertion with increasing atomic mass of the chalcogen atom X. While the electronic conductivity increases with increasing ion concentration at low concentrations, we do not observe a (positive) conductivity jump at the phase transition from H to T’.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Controlling magnetic exchange and anisotropy by nonmagnetic ligand substitution in layered 𝑀⁢P⁢𝑋 3 (𝑀 = Ni, Mn; 𝑋 = S, Se)

Recent discoveries in two-dimensional magnetism have intensified the investigation of van der Waals magnetic materials and further improved our ability to tune their magnetic properties. Tunable magnetism has been widely studied in antiferromagnetic metal thiophosphates 𝑀⁢P⁢𝑋 3 . Substitution of metal ions 𝑀 has been adopted as an important technique to engineer the magnetism in 𝑀⁢P⁢𝑋 3 . In this work, we have studied the previously unexplored chalcogen 𝑋 substitutions in 𝑀⁢P⁢𝑋 3 (𝑀 = Mn/Ni; 𝑋 = S/Se). We synthesized the single crystals of MnP⁢S 3−𝑥 ⁢Se 𝑥 (0 ≤ 𝑥 ≤ 3) and NiP⁢S 3−𝑥 ⁢Se 𝑥 (0 ≤ 𝑥 ≤ 1.3) and investigated the systematic evolution of the magnetism with varying 𝑥. Our study reveals the effective tuning of magnetic interactions and anisotropies in both MnPS 3 and NiPS 3 upon Se substitution. Such efficient engineering of the magnetism provides a suitable platform to understand the low-dimensional magnetism and develop future magnetic devices.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2022

Novel Functional Thermal Energy Storage Materials for Buildings Applications

The leakage of solid-liquid phase change materials (PCMs) tremendously limits their long-term application in thermal energy storage (TES). In this work, we present durable and form-stable shape-stabilized PCMs (ss-PCMs) for TES in building envelopes. These ss-PCMs are fabricated by encapsulating polyethylene glycol (PEG) consisting of different molecular weights within mesoporous magnesium oxide and silica dioxide. For the first time, the phase transition temperature (Tt) of ss-PCMs has been fine-tuned synthetically to be comfortable to building occupants by utilizing PEG blends with molecular weights of 600 and 800 g/mol. Several parameters, including surface hydrophilicity/hydrophobicity, surface area, and PCM loading percentage, have been studied to maximize the latent heat enthalpy for high energy efficiency and maintain form stability. The best ss-PCM candidate with suitable Tt and appreciable latent heat enthalpy exhibits a repeatable phase change behavior for up to 1,000 thermal cycles without leakage, which provides a promising solution for durable TES in buildings. The Tt tunability extends its application over a wider temperature range beyond buildings.

building envelope↗
DOE OSTI2021

Recent Advances in Vertically Aligned Nanocomposites with Tunable Optical Anisotropy: Fundamentals and Beyond

Developing reliable and tunable metamaterials is fundamental to next-generation optical-based nanodevices and computing schemes. In this review, an overview of recent progress made with a unique group of ceramic-based functional nanocomposites, i.e., vertically aligned nanocomposites (VANs), is presented, with the focus on the tunable anisotropic optical properties. Using a self-assembling bottom-up deposition method, the as-grown VANs present great promise in terms of structural flexibility and property tunability. Such broad tunability of functionalities is achieved through VAN designs, material selection, growth control, and strain coupling. The as-grown multi-phase VAN films also present enormous advantages, including wafer scale integration, epitaxial quality, sharp atomic interface, as well as designable materials and geometries. This review also covers the research directions with practical device potentials, such as multiplex sensing, high-temperature plasmonics, magneto-optical switching, as well as photonic circuits.

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

Monomer-scale design of functional protein polymers using consensus repeat sequences

Protein-based polymers possess chemically defined sequences that can encode diverse properties and functions into a new class of biopolymeric materials. However, sequence variation that emerges from evolution can obscure the sequence–function relationships of naturally derived polymers. One strategy to clarify these relationships is to identify common sequences between proteins with similar functions. These conserved sequences often emerge from repeat proteins, and “consensus repeat sequences” provide a convenient platform for systematic investigations of biopolymer sequence–property relationships. In this review, we highlight recent approaches to engineer tunable polymeric materials using monomer-scale design of consensus repeat proteins. Here, we explore established and emerging protein-based materials with mechanical resilience, thermodynamic phase behavior, chemical responsiveness, biomolecular transport, and hierarchical structure. Overall, recent advances in the monomer-scale design of repetitive protein polymers present exciting fundamental and translational opportunities for polymer scientists and engineers.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Broadband and Tunable Microwave Absorption Properties from Large Magnetic Loss in Ni–Zn Ferrite

Highly effective electromagnetic (EM) wave absorber materials with strong reflection loss (RL) and a wide absorption bandwidth (EBW) in gigahertz (GHz) frequencies are crucial for advanced wireless applications and portable electronics. Traditional microwave absorbers lack magnetic loss and struggle with impedance matching, while ferrites are stable, exhibit excellent magnetic and dielectric losses, and offer better impedance matching. However, achieving the desired EBW in ferrites remains a challenge, necessitating further composition design. In this study, impedance matching is successfully enhanced and EBW in Ni–Zn ferrite is broadened by successive doping with Mn and Co , without incorporation of any polymer filler. It is found that Ni 0.4 Co 0.1 Zn 0.5 Fe 1.9 Mn 0.1 O 4 material exhibits exceptional EM wave absorption, with a maximum RL of −48.7 dB. It also featured a significant EBW of 10.8 GHz, maintaining a 90% absorption rate (RL < −10 dB) for a thickness of 4.5 mm. These outstanding properties result from substantial magnetic losses and favorable impedance matching. These findings represent a significant step forward in the development of microwave absorber materials, addressing EM wave pollution concerns within GHz frequencies, including the frequency band used in popular 5G technology.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Method of tuning physical properties of thermosets

Polymerization-induced phase separation enables fine control over thermoset network morphologies, yielding heterogeneous structures with domain sizes tunable over 1-100 nm. However, the controlled chain-growth polymerization techniques exclusively employed to regulate morphology at these length scales are unsuitable for most thermoset materials typically formed through step-growth mechanisms. By employing binary mixtures in place of the classic constituents of phase-separating thermosets—resin, curing agent, and secondary polymer—facile tunability over morphology can be achieved through a single compositional parameter. Indeed, this method yields morphologies spanning nano-scale to macro-scale, controlled by the relative reactivities and thermodynamic compatibility of the network components. Due to the connection between chain dynamics and microstructure in these materials, the tunable morphology enables exquisite control over glass transition and other physical and mechanical properties.

Jones, Brad Howard↗
DOE OSTI2020

Utilizing Site Disorder in the Development of New Energy-Relevant Semiconductors

We report controlling site disorder in ternary and multinary compounds enables tuning optical and electronic properties at fixed lattice constants and stoichiometries, moving beyond many of the challenges facing binary alloy systems. Here, we consider possible enhancements to energy-related applications through the integration of disorder-tunable materials in devices such as light-emitting diodes, photonics, photovoltaics, photocatalytic materials, batteries, and thermoelectrics. However, challenges remain in controlling and characterizing disorder. Focusing primarily on II–IV–V 2 materials, we identify three metrics for experimentally characterizing cation site disorder. Complementary to these experiments, we discuss simulation methods to understand disordered materials. Nonidealities, such as off-stoichiometry and oxygen incorporation, can occur while synthesizing metastable disordered materials. While nonidealities may seem undesirable, we describe how if harnessed they could provide another knob for tuning disorder and subsequently properties. To illustrate the effects of disorder on device-relevant properties, we provide case examples of disordered materials and their potential in device applications.

36 MATERIALS SCIENCE↗
DOE OSTI2021

A Fabrication Strategy for Reconfigurable Millimeter–Scale Metamaterials

Rather than depending on material composition to primarily dictate performance metrics, metamaterials can leverage geometry to achieve specific properties of interest. For example, reconfigurable metamaterials have enabled programmable shape transformations, tunable mechanical properties, and energy absorption. While several methods exist to fabricate such structures, they often place severe restrictions on manufacturing materials, or require significant manual assembly. Moreover, these arrays are typically composed of unit cells that are either macro–scale or micro–scale in dimension. Here, the fabrication gap is bridged, and laminate manufacturing is used to develop a method for designing reconfigurable metamaterials at the millimeter–scale, that is compatible with a wide range of materials, and that requires minimal manual assembly. In addition to showing the versatility of this fabrication method, how the use of laminate manufacturing affects the behavior of these multi–component arrays is also characterized. To this end, a numerical model that captures the deformations exhibited by the structures is developed, and an analytic model that predicts the strain of the structure under compressive stress is built. Overall, this approach can be leveraged to develop millimeter–scale metamaterials for applications that require reconfigurable materials, such as in the design of tunable acoustics, photonic waveguides, and electromagnetic devices.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Discovery of two-dimensional binary nanoparticle superlattices using global Monte Carlo optimization

Binary nanoparticle (NP) superlattices exhibit distinct collective plasmonic, magnetic, optical, and electronic properties. Here, we computationally demonstrate how fluid-fluid interfaces could be used to self-assemble binary systems of NPs into 2D superlattices when the NP species exhibit different miscibility with the fluids forming the interface. We develop a basin-hopping Monte Carlo (BHMC) algorithm tailored for interface-trapped structures to rapidly determine the ground-state configuration of NPs, allowing us to explore the repertoire of binary NP architectures formed at the interface. By varying the NP size ratio, interparticle interaction strength, and difference in NP miscibility with the two fluids, we demonstrate the assembly of an array of exquisite 2D periodic architectures, including AB-, AB 2 -, and AB 3 -type monolayer superlattices as well as AB-, AB 2 -, A 3 B 5 -, and A 4 B 6 -type bilayer superlattices. Our results suggest that the interfacial assembly approach could be a versatile platform for fabricating 2D colloidal superlattices with tunable structure and properties.

36 MATERIALS SCIENCE↗