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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 OSTI2023

N2-to-NH3 conversion by excess electrons trapped in point vacancies on 5f-element dioxide surfaces

Ammonia (NH 3 ) is one of the basic chemicals in artificial fertilizers and a promising carbon-free energy storage carrier. Its industrial synthesis is typically realized via the Haber−Bosch process using traditional iron-based catalysts. Developing advanced catalysts that can reduce the N 2 activation barrier and make NH 3 synthesis more efficient is a long-term goal in the field. Most heterogeneous catalysts for N 2 -to-NH 3 conversion are multicomponent systems with singly dispersed metal clusters on supporting materials to activate N 2 and H 2 molecules. Herein, we report single-component heterogeneous catalysts based on 5 f actinide dioxide surfaces (ThO 2 and UO 2 ) with oxygen vacancies for N 2 -to-NH 3 conversion. The reaction cycle we propose is enabled by a dual-site mechanism, where N 2 and H 2 can be activated at different vacancy sites on the same surface; NH 3 is subsequently formed by H − migration on the surface via associative pathways. Oxygen vacancies recover to their initial states after the release of two molecules of NH 3 , making it possible for the catalytic cycle to continue. Our work demonstrates the catalytic activities of oxygen vacancies on 5 f actinide dioxide surfaces for N 2 activation, which may inspire the search for highly efficient, single-component catalysts that are easy to synthesize and control for NH 3 conversion.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Generalized optimization-based synthesis of membrane systems for multicomponent gas mixture separation

Synthesizing a membrane system to separate multicomponent gas mixture is challenging due to the combinatorial number of feasible configurations and the difficulties in describing the multicomponent permeators. Here we present a mixed-integer nonlinear programming (MINLP) model for synthesizing membrane systems for multicomponent gas mixture separation. The approach employs a richly connected superstructure to represent numerous potential system configurations, and different physics-based surrogate permeator models, such as countercurrent flow or crossflow, to be used in each stage. Moreover, to describe realistic systems, pressure drop equations can be included. We also present solution methods to accelerate the solution process. Through a case study of natural gas sweetening, we demonstrate that the proposed approach is able to obtain good solutions using an off-the-shelf global optimization solver. Finally, we expand the conventional membrane system synthesis problem by introducing feed variability in our model through a case study of an integrated reactor-separation system.

42 ENGINEERING↗
DOE OSTI2026

Absorption dissymmetry factor enhancement: A data-driven approach to unravel the synthesis knobs of chiral 2D perovskites

Chiral 2D metal halide perovskites (MHPs) are promising for spin-optoelectronic applications, yet their absorption dissymmetry factor (g abs ) exhibits significant variability due to complex, co-dependent structural and experimental factors. Here, we established a data-driven framework using Pearson’s correlation, ANOVA, and Gaussian process regression to identify and model key synthesis “knobs” governing these properties. The analysis revealed that solvent choice is the primary factor driving variability. For acetonitrile-based films, g abs was maximized by optimizing annealing temperature and film thickness. Conversely, films from higher boiling point solvents showed complex dependencies on annealing temperature, excitonic integral intensity, and film texture. These statistical correlations provide a roadmap for the rational design of high-performance chiral MHPs and establish a foundation for future machine learning-driven material exploration.

ANOVA↗
DOE OSTI2022

Optimizing thermal stability and mechanical behavior in segregation-engineered nanocrystalline Al–Ni–Ce alloys: A combinatorial study

The deliberate use of solute enrichment at grain boundaries, otherwise known as segregation engineering, is a promising approach to tailor the properties of interface-dominated materials such as nanocrystalline alloys. Here, the ensuing chemical and structural evolution at grain boundaries can give rise to thermal stability and excellent mechanical properties, but the interplay between enrichment, phase decomposition, grain growth, and mechanical behavior exists in a vast composition and processing space. In this study, a combinatorial synthesis and rapid characterization approach was applied to segregation-engineered nanocrystalline Al–Ni–Ce alloys to assess the evolution of microstructure and resulting mechanical behavior as functions of alloying content and annealing conditions. In addition to the identification of alloys and processing conditions that give rise to exceptional thermal stability, strength retention, and homogeneous plastic flow, we construct combined thermal stability and deformation mechanism maps that demarcate several important regimes of behavior.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Site-specific surface reactivity on SnO 2 : Evaluating selective atomic layer deposition processes

Area selective atomic layer deposition (AS-ALD) is a bottom-up synthesis approach with potential for deposition with molecular level precision. Here, the site-specific hydration of metal oxide substrates, combined with surface H 2 O-selective ALD processes, provides a potentially powerful path to targeted synthesis. Density functional theory (DFT) calculations are used to predict the thermodynamics of ALD precursor reactivity and hydration for (001), (101), (110), and (100) rutile SnO 2 facets as a function of temperature. Trimethylaluminum (TMA) and dimethyl aluminum isopropoxide (DMAI) dimers are predicted to react with both dehydrated and hydrated SnO 2 (001), (101), and (110) facets at ALD-relevant temperatures, while the SnO 2 (100) facet is predicted to be uniquely unreactive with TMA and DMAI monomers as well as dehydrate near 177 °C making this facet more amenable to targeted ALD. In situ ellipsometric studies of Al 2 O 3 ALD on polycrystalline SnO 2 at 150 °C are consistent with the computational predictions of rapid and unselective nucleation, in stark contrast to inhibited and selective ALD on isostructural rutile TiO 2 .

Atomic Layer Deposition↗
DOE OSTI2025

Machine-Learned Force Field for Molecular Dynamics Simulations of Nonequilibrium Ammonia Synthesis on Iron Catalysts

Ammonia (NH 3 ) is one of the most important industrial chemicals. The conventional NH 3 synthesis method-the Haber–Bosch process-converts atmospheric nitrogen (N 2 ) into NH 3 using H 2 with an iron (Fe) catalyst. However, this process requires high pressures (100–200 atm) and temperatures (700–800 K) near thermal equilibrium. Recently, Fe-based nanocatalysts have been reported to produce promising NH 3 yields under atmospheric pressures and temperature-modulated nonequilibrium conditions. Understanding the mechanism of nonequilibrium catalysis with programmed temperature variation could help to optimize this fully electrified and less energy-intensive process. Although reactive molecular dynamics (RMD) simulations can be a useful tool to model nonequilibrium catalytic processes, they require the development of accurate force fields (i.e., interatomic potentials). Here, we present a machine-learned (ML) force field within the Deep Potential MD (DPMD) framework, trained using periodic density functional theory (DFT) calculations, to model NH 3 synthesis on Fe catalysts with various surface adsorbates such as *N, *H, *N 2 , *H 2 , *NH, *NH 2 , and *NH 3 . Here, we generated the DFT data from static models of elementary reactions on the most stable (110) surface of body-centered cubic Fe, which then were augmented by data from constant number of particles–volume–temperature (NVT) DFT-MD trajectories at various temperatures. Finally, we utilized the fully optimized ML force field to investigate reaction dynamics at an Fe(110) surface at linearly increasing temperatures using NVT-DPMD simulations. Our simulations indicate that pulsed temperature ramping could prove favorable for NH3 synthesis. For example, we conducted ramping under multiple sets of conditions: (i) from 900 to 1200 K over periods of 0.1–0.3 ns for Fe surfaces precovered with N or NH along with H; and (ii) from 300 to 600 K over 0.1–0.3 ns for Fe surfaces precovered with NH 3 . While our simulations so far are limited to short time scales (very rapid heating), these observations shed light on the mechanism of the high NH 3 synthesis rate achieved in a novel temperature-modulated nonequilibrium catalytic reactor using pulsed heating and cooling.

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

Speaker-targeted Synthetic Speech Detection

Text-to-speech technologies are evolving quickly towards realistic-sounding human-like voices. As this technology improves, so does the opportunity for malpractice in speaker identification (SID) via spoofing, the process of impersonating a voice biometric via synthesis. More data typically equates to a more realistic voice model, which poses an issue for well-known subjects, such as politicians and celebrities, who have vast amounts of multimedia available online. Detection of synthetic speech has relied on signal processing techniques that focus on the generation of new acoustic features and train deep learning models to detect when an audio file has been manipulated through the characterization of unnatural changes or artifacts. However, these techniques do not use any information from the speaker they are evaluating. This paper proposes to incorporate information from the speaker-of-interest (SoI) into the models to avoid specific spoofing attacks for certain vulnerable people. The wealth of data for well-known people can also be used to train a speaker-specific spoofing detector with a higher level of accuracy than a speaker-independent model. The paper proposes a new xResNet-PLDA system and compares it to three different baseline systems: a state-of-the-art speaker identification system, an xResNet system trained to discriminate between bona fide and fake speech, and a speaker identification system in which the PLDA and calibration models were trained with bona fide and fake speech. We evaluated the systems in two different scenarios — a cross-validation scenario and a hold-out scenario — with three different databases. We show how the proposed system outperforms dramatically the baseline systems in each scenario and for each database. Finally, we show how using a small amount of the SoI’s speech to adapt global calibration parameters improves the performance of the system, especially in unseen conditions.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2020

Improving the picture of atomic structure in nonoriented polymer domains using the pair distribution function: A study of polyamide 6

Abstract Investigations of the atomic structures within polyamides started over 80 years ago and continue today. These weakly ordered materials diffract X‐rays poorly and typically require postprocessing to obtain idealized samples for structural studies. An important goal remains to develop techniques to study the local structure in its natural state, with atomic resolution, and with sensitivity to subtle changes due to synthesis conditions or other technologically relevant processing procedures. Here, we compare the structures of as‐produced, nonoriented polyamide 6 ([C 6 H 11 NO] n ) from both hydrolytic and anionic processes. A total scattering pair distribution function approach is used to elucidate information about the atomic bonding, molecular conformation, chain packing, crystallite size, and ratio of ordered to disordered domain content. The results are compared with those from standard analytical methods.

Terban, Maxwell W.↗
DOE OSTI2024

Computationally guided synthesis of carbon coated mesoporous silica materials

Mesoporous silica materials (MSMs) are well-suited for biomedical applications due to their unique features, including a large surface area and tunable pore size. To enhance their durability, the small pores in MSMs are filled with carbon precursors and then carbonized to prevent them from interacting with unreacted silicic acid. Here, in this study, we synthesized and healed MSMs using a combination of non-reactive and reactive molecular dynamics (MD) simulations. The non-reactive MD simulation revealed that the self-assembly of Pluronic® L64 polymers in water resulted in nearly 80 % hydrogen bonds between the hydrophilic sections of the micelle and water. In the bond-boosted ReaxFF MD simulations, silicic acid precursors were condensed on the micelle surface, with over 60 % of them leading to the creation of periodic mesoporous silica within the system. Condensation of silicic acid precursors at 300 K with bond-boosting and at 1500 K without it both significantly promoted the polymerization of Si(OH) 4 , with the latter doubling the rate compared to the former. Subsequently, we healed the MSM surface by carbonizing carbon precursors inside an MSM pore. Polyethylene (PE) and high-rank lignite were identified as the most suitable precursors due to their ability to form turbostratic graphene structures. High-rank lignite exhibited the highest carbon conversion ratio to 6-membered rings, closely followed by PE, in the carbon ring formation analysis. Additionally, the production of gases, such as H 2 , increased significantly for PE at both 2200 K and 2600 K, indicating the conversion of a considerable portion of carbon into graphitic or turbostratic structures. The carbonization of PE primarily led to the formation of planar (sp 2 ) structures, while sucrose yielded the least planar structures. Finally, we studied the protective blocking of unreacted silicic acid precursor by considering a PET turbostratic graphene structure in a silica mesopore formed at 2600 K. The trajectory analysis showed that the surface of the silica was effectively coated with PET tar, preventing unreacted silicic acid from interacting with the inner silica pore surface. These findings offer valuable insights into the synthesis and carbonization-based healing processes of MSMs, enhancing their potential for various biomedical applications.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Compact and accurate chemical mechanism for methane pyrolysis with PAH growth

In this study, a reliable and compact chemical mechanism of gas-phase methane pyrolysis leading to formation of large polycyclic aromatic hydrocarbon (PAH) molecules has been developed. This model is designed for studies of carbon nanostructure synthesis such as carbon black and graphene flakes, including soot growth kinetics. Methane pyrolysis with carbon nanostructure synthesis is a two-stage process where conversion of CH 4 to C 2 H 2 precedes the growth of PAH molecules from acetylene. We present a single chemical mechanism that accurately describes both stages. We have constructed a compact and accurate chemical mechanism capable of modeling both stages of methane pyrolysis based on the ABF mechanism which was expanded with the most prominent reaction pathways from the mechanism by Tao for small PAH molecules and HACA pathways for larger PAH molecules, up to 37 aromatic rings. The resulting mechanism was validated through comparison to multiple available sets of experimental data. Good agreement with the experimental data for both processes was obtained. Performance of the mechanism was tested for pyrolysis of methane-rich mixtures under long residence times leading to abundant formation of PAH molecules. It is shown that the inclusion of larger PAH species (up to A37) in the chemical mechanism is important for accurate prediction of the fraction of carbon converted to PAH molecules and, correspondingly, the residual fraction of acetylene in the mixture. The mechanism file is available upon request.

08 HYDROGEN↗
DOE OSTI2023

Piezo-electrocatalytic oxidation of methanol with UV-ozone treated wurtzite zinc oxide nanostructures

Leveraging mechanically-induced piezoelectric polarization, piezocatalysis emerges as a viable mechanism for enhancing the efficiency of catalytic processes. Nanostructured, catalytically active, rationally designed piezoelectric semiconductors can achieve high-performance catalysts for various applications using cost-effective electrocatalytic pathways, such as mechanical stimuli. We design and demonstrate for the first time a cost-effective, high-performance piezo-electrocatalyst for anodic methanol oxidation, which is crucial for the practical application and deployment of direct methanol fuel cells in a variety of emerging clean energy technologies. We synthesized wurtzite ZnO nanorods and nanosheets treated with UV-O 3 to characterize and compare their efficacy for piezo-electrocatalytic methanol oxidation. The generation of piezoelectric polarization charges in nanostructured semiconducting ZnO catalysts significantly increased their electrocatalytic performance. By elucidating the charge transfer between mechanically-deformed ZnO nanostructures and methanol molecules, we identified the underlying mechanism for the piezo-electrocatalytic process for methanol oxidation. The facile synthesis of high-quality ZnO nanostructures enables low-cost, scalable manufacture and direct integration into electrocatalysts whose performance could be enhanced by harvesting mechanical energy that would otherwise be wasted in the working environment.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2020

NMR-Guided High-Temperature Electrolyte Design Using a Novel PF 5 Marker

The thermal degradation of electrolytes containing lithium hexafluorophosphate (LiPF 6 ) is a well-studied subject. However, practical application of the knowledge is difficult since the effects of the degradation process on battery performance are not well known. In this work, we propose a novel NMR experimental setup allowing direct observation of the effects of various perturbations on the electrolyte thermal degradation process, which guides the design and synthesis of new additives that improve lithium-ion battery performance at elevated temperatures.

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

Surface Basic Site Effect on Boron-Promoted Platinum Catalysts for Dry Reforming of Methane

Platinum has been shown to be an active catalyst for the dry reforming of methane (DRM), which converts CO 2 and CH 4 into 2CO and 2H 2 (synthesis gases) that can further be processed to produce valuable chemical feedstocks. Catalytic activity is often improved by the addition of promoter atoms, which are typically transition metals or noble metals, such as PtNi and PtSn. Recently, boron has shown to be an effective and low-cost catalyst promoter. Pt/B/SiO 2 catalysts were prepared for DRM catalysis and compared with Pt/SiO 2 catalysts without boron promotion. Both catalysts had similar surface concentrations of platinum, but the catalytic activity at 750 °C after 14 h for boron-containing catalyst was very high, resulting in nearly 100% CO 2 conversion and a H 2 /CO ratio close to unity, compared to 12% CO 2 conversion and H 2 /CO of 0.35 for boron-free Pt/SiO 2 . The catalysts were investigated with X-ray absorption spectroscopy (XAS), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Fourier-transform infrared spectroscopy (FTIR), and CO 2 temperature-programmed desorption (CO 2 -TPD) to identify the deactivating factors. It was determined that neither platinum nanoparticle sintering nor coking was a significant factor in catalyst deactivation; instead, boron had an effect on the reactive surface groups on the SiO 2 support. Finally, these surface groups, such as hydroxyls and surface basic sites, enhance the adsorption of CO 2 and potentially stabilize intermediate carbonate species, resulting in a high CO 2 conversion for boron-promoted platinum catalysts.

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

Understanding Solvent-Induced Glass Transition in Polymer Thin Films Using Absorption–Desorption Isotherms

The fundamental thermodynamic and mechanical underpinnings of polymer thin films exposed to solvent vapor are critical for the development of advanced nanolithography and high-performance coatings. This work investigates the solvent− polymer interactions of glassy thin films by using the solvent absorption−desorption isotherms. An analogous relationship to the Flory−Fox equation was observed between solvent−induced glass transition, swelling, Flory−Huggins interaction parameter, and molecular weight. Isothermal swelling measurements revealed that the glass transition trends are more robust in the absorption curve compared to desorption, contrary to previous reports. Excess osmotic pressure analysis of the isotherm provides a measure of the degree of physical aging in thin films annealed below the glass transition. This is further validated in the ordering of block copolymer (BCP) films annealed at low solvent activity. In agreement with the thermal analysis, free-surface plasticization effects become the most prominent below 100 nm. However, solvent annealing is largely dependent on solvent mass transport, as made evident by the strong dependence on solvent viscosity. From these observations, four general types of isotherms are identified that graphically capture distinct solvent−polymer interaction regimes. More broadly, these results inform solvent vapor annealing-induced self-assembly, sequential infiltration synthesis, membrane-based separations, adsorptive processes, and swelling-based responsive materials design.

Hendeniya, Nayanathara [Iowa State Univ., Ames, IA↗
DOE OSTI2021

Oxidative Dehydrogenation of Propane to Propylene with Soft Oxidants via Heterogeneous Catalysis

Oxidative dehydrogenation of propane to propylene can be achieved using conventional, oxygen-assisted dehydrogenation of propane (O 2 –ODHP) or via the use of soft oxidants, such as CO 2 , N 2 O, S-containing compounds, and halogens/halides. The major roles of soft oxidants include inhibiting overoxidation and improving propylene selectivity, which are considered to be current challenges in O 2 -assisted dehydrogenation. For both CO 2 – and N 2 O–ODHP reactions, significant efforts have been devoted to developing redox-active (e.g., chromium, vanadate, iron, etc.), nonredox-type main group metal oxide (e.g., group IIIA, gallium), and other transition metal/metal oxide catalysts (e.g., molybdenum, palladium platinum, rhodium, ruthenium, etc.), as well as zeolite-based catalysts with adjustable acid–base properties, unique pore structures, and topologies. Metal sulfides have shown promising performance in DHP, whereas the development of suitable catalysts has lagged for SO 2 - or S-assisted ODHP. Recently, significant efforts have been focused on homogeneous and heterogeneous ODHP using halogens (e.g., Br 2 , I 2 , Cl 2 , etc.) and hydrogen halides (e.g., HCl and HBr) for the development of facile processes for C 3 H 6 synthesis. This work aims to provide a critical, comprehensive review of recent advances in oxidative dehydrogenation of propane with these soft oxidants, especially highlighting the current state of understanding of the following factors: (i) relationships between composition, structure, and catalytic performance, (ii) effects of the support, acidity, and promoters, (iii) reaction pathway and mechanistic insights, and (iv) the various roles of soft oxidants. Theoretical and computational insights toward understanding reaction mechanisms and catalyst design principles are also covered. Future research opportunities are discussed in terms of catalyst design and synthesis, deactivation and regeneration, reaction mechanisms, and alternative approaches.

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

Optimized Photoemission from Organic Molecules in 2D Layered Halide Perovskites

In recent years, hybrid organic−inorganic metal halides have been at the forefront of materials research. Typically, the functional (e.g., optoelectronic) properties of hybrid halides are derived from the inorganic structural part, whereas the organic structural units can add extra advantages in terms of stability, rigidity, and processability. Here, we report the design, synthesis, and characterization of two new hybrid materials in which the outstanding photophysical properties originate from the organic structural part. The new compounds, (C 15 H 16 N) 2 CdCl 4 and ((Br)C 15 H 15 N) 2 CdCl 4 , have 2D layered Ruddlesden−Poppertype perovskite structures. These hybrids are blue-white light emitters just like their corresponding pure organic salts, but with much improved emission efficiencies. Optical spectroscopy and density functional theory (DFT) studies confirm that photoemission comes from the trans-stilbene organic cations. The photoluminescence quantum yield (PLQY) values of these new materials are among the highest known, 50.83% and 26.60% for (C 15 H 16 N) 2 CdCl 4 and ((Br)C 15 H 15 N) 2 CdCl 4 , respectively. This is up to a 5-fold increase as compared to the light emission efficiency of the precursor salt C 15 H 16 NCl (PLQY of 10.33%). Alongside their outstanding optical properties, their environmental and thermal stability allow their consideration for potential practical applications such as radiation detection. This work shows that hybrid metal halides can be compositionally and structurally engineered to have highly efficient photoemission originating from the organic components for fast scintillation applications.

Halogens↗
DOE OSTI2020

Preparation of cyclohexene isotopologues and stereoisotopomers from benzene

The hydrogen isotopes deuterium (D) and tritium (T) have become essential tools in chemistry, biology and medicine1. Beyond their widespread use in spectroscopy, mass spectrometry and mechanistic and pharmacokinetic studies, there has been considerable interest in incorporating deuterium into drug molecules1. Deutetrabenazine, a deuterated drug that is promising for the treatment of Huntington’s disease2, was recently approved by the United States’ Food and Drug Administration. The deuterium kinetic isotope effect, which compares the rate of a chemical reaction for a compound with that for its deuterated counterpart, can be substantial1,3,4. The strategic replacement of hydrogen with deuterium can affect both the rate of metabolism and the distribution of metabolites for a compound5, improving the efficacy and safety of a drug. The pharmacokinetics of a deuterated compound depends on the location(s) of deuterium. Although methods are available for deuterium incorporation at both early and late stages of the synthesis of a drug6,7, these processes are often unselective and the stereoisotopic purity can be difficult to measure7,8. Here we describe the preparation of stereoselectively deuterated building blocks for pharmaceutical research. As a proof of concept, we demonstrate a four-step conversion of benzene to cyclohexene with varying degrees of deuterium incorporation, via binding to a tungsten complex. Using different combinations of deuterated and proteated acid and hydride reagents, the deuterated positions on the cyclohexene ring can be controlled precisely. In total, 52 unique stereoisotopomers of cyclohexene are available, in the form of ten different isotopologues. This concept can be extended to prepare discrete stereoisotopomers of functionalized cyclohexenes. Such systematic methods for the preparation of pharmacologically active compounds as discrete stereoisotopomers could improve the pharmacological and toxicological properties of drugs and provide mechanistic information related to their distribution and metabolism in the body.

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

The effect of chemically preintercalated alkali ions on the structure of layered titanates and their electrochemistry in aqueous energy storage systems

We introduce a novel chemical preintercalation synthesis technique based on a hydrogen peroxide induced sol–gel process to obtain alkali ion containing ternary layered titanates (MTO, where M = Li, Na, K). Synthesis parameters leading to the formation of single-phase materials with homogeneous elemental distribution are reported for each of the preintercalated ions. Our analyses indicate that the interlayer spacing in the structure of the layered titanates increases with the increase of the radius of the hydrated preintercalated ion. Scanning and transmission electron microscopy imaging revealed morphological diversity: the LTO phase crystallized as nanoplates assembled in “peony-like” spherical agglomerates while NTO and KTO particles exhibited a one-dimensional nanobelt or wire-like morphology, with the KTO nanobelts being shorter and more aggregated than the NTO nanobelts. Structural refinement corroborated by electron diffraction and high-resolution transmission electron microscopy revealed that the structure of the LTO phase is built by stacking Ti–O layers containing a single straight layer of connected TiO 6 octahedra. The layers in NTO and KTO structures form differently and consist of double Ti–O layers with two titanium rows and ragged arrangement of units built by TiO6 octahedra. The NTO electrodes exhibited the highest electrochemical performance in cells with aqueous 1 M Na 2 SO 4 electrolyte, followed by the KTO electrodes and then LTO electrodes, and this trend is maintained at various scan rates. The established relationships between the structure and electrochemical performance reveal that, in addition to interlayer distance and chemistry of the interlayer region, the structure of the layers can play an important role in charge storage properties of layered oxide electrodes. The double Ti–O layers in the structure of NTO and KTO phases provide a larger number of redox centers which could contribute to the superior electrochemical performance as compared to the LTO electrodes. Our findings indicate that layered materials containing double transition metal oxide layers are promising candidates for exfoliation and assembly with electronically conductive layers with the aim to create 2D heterostructures with high electrochemical performance.

25 ENERGY STORAGE↗