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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 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Elucidating Sodium-Sulfur Battery Chemistry using Operando Transmission X-ray Microscopy and X-ray Absorption Spectroscopy

Room-temperature sodium-sulfur (Na-S) batteries offer a beneficial and cost-effective solution for powering modern electric grids and devices. However, Na-S batteries suffer from performance decay during battery cycling due to the sluggish kinetics and polysulfide shuttling. Revealing the conversion mechanism of the Na-S chemistry is critical to designing high-capacity and stable Na-S batteries. In this study, we employed operando X-ray microscopy and operando X-ray absorption spectroscopy to elucidate the sulfur conversion in a carbon host using an ether-based electrolyte. We reveal the structural and chemical evolution of the sulfur cathode during cycling, which results in volume expansion and the dissolution of active material, ultimately affecting the battery performance. Our work provides fundamental insight into the sulfur reaction scheme, addressing the lingering challenges before establishing inexpensive Na-S batteries for broad applications, including portable electronics and large-scale energy storage.

Jagadeesan, Sathya Narayanan [SLAC National Accele↗
DOE OSTI2022

Manufacturing Bulk Nanocrystalline Al-3Mg Components Using Cryomilling and Spark Plasma Sintering

In the current study, pure aluminum (Al) powders were cryomilled with and without 3 wt.% pure magnesium (Mg) dopant for varying durations followed by spark plasma sintering (SPS) of powders to prepare bulk components with superior mechanical properties. The crystallite sizes were determined for powders and the bulk components by analyzing the X-ray diffraction (XRD) spectrum. The calculations indicated a reduction in crystallite size with the increase in the cryomilling duration. The results also showed a more significant decrease in the crystallite sizes for Al-3Mg samples than that of pure Al. The changes in the surface morphology of powders were characterized using scanning electron microscopy (SEM). The elemental mapping analysis at nanoscale was carried out using Energy-dispersive X-ray spectroscopy (EDX) in Scanning transmission electron microscopy (STEM). The mechanical properties of the bulk components were assessed using a Vickers Microhardness tester. The test results demonstrated an improvement in the hardness of Mg-doped components. Higher hardness values were also reported with an increase in the cryomilling duration. This article discusses the mechanisms for the reduction in crystallite size for pure Al and Al-3Mg and its subsequent impact on improving mechanical properties.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Dynamic Molecular Investigation of the Solid-Electrolyte Interphase of an Anode-Free Lithium Metal Battery Using In Situ Liquid SIMS and Cryo-TEM

Solid electrolyte interphase (SEI) has been widely perceived to play a critical role in the stable cycling of rechargeable batteries. However, associated with the fragile and air-sensitive nature of the SEI layer, delineation of the formation process and the nature of SEI remains a big challenge. Here, we use in situ liquid time-of-flight secondary ion mass spectroscopy (TOF-SIMS), cryo- transmission electron microscope (TEM) and density functional theory (DFT) calculation to delineate molecular process on the formation of SEI layer under the dynamic operating condition. We discover that the onset potential for SEI layer formation and the thickness of the SEI show dependence on the solvation shell structure. Using LiCoO 2 as a cathode and Cu film as an anode, the SEI is noticed to start to form at around 2.0 V and reach its final thickness (irreversible part, ~ 40-50 nm) at about 3.0 V in the 1 M LiPF 6 –EC/DMC electrolyte, while for the case of 1 M LiFSI–DME, the SEI starts to form at around 1.5 V and reaches its final thickness (~ 20 nm) at about 2.0 V. The in situ TOF-SIMS clearly indicates the outer SEI layer formation and dissipation upon charging and discharging, implying a continued evolution of electrolyte structure with extended cycling. In conclusion, the present work establishes a direct correlation between the molecular signature of SEI layer with solvation feature of electrolytes in lithium batteries, providing insights for tailoring SEI layer toward improved electrochemical properties of lithium batteries.

25 ENERGY STORAGE↗
DOE OSTI2021

EBSD of Rough Native CuInGaSe2 Thin-Films

The polycrystalline Cu (In, Ga) Se2, or CIGS, based thin-film materials system has long been studied for use in photovoltaic technologies, where its bandgap tunability, mechanical flexibility, and relatively low production costs are all appealing. Nonetheless, significant defect populations, which serve to reduce efficiency, create performance instabilities, and increase concerns about long-term reliability, have hindered wide-scale adoption. Prior work, including application of a scanning probe based deep level trap spectroscopy (SP-DLTS) defect mapping technique and scanning transmission electron microscope (STEM) based electron energy loss spectroscopy (EELS), has shown that the most detrimental defects, with energy level near mid-gap (thus serving as a carrier recombination center), are most likely caused by CuIn/Ga antisites and tend to cluster at or around certain grain boundaries [1,2]. However, the exact nature of these particular boundaries — their structures, chemistries, or even the relative misorientation of their associated grains — and their relation to this defect clustering and/or its formation is yet unknown. As such, electron backscatter diffraction (EBSD) orientation mapping, directly correlated with defect-sensitive techniques like SP-DLTS and/or STEM-EELS, could prove critical for providing the final missing links toward understanding the mechanisms behind these defects. Indeed, recent studies using correlative electron beam induced current (EBIC) with EBSD have been able to identify boundaries, and their relative misorientations, that possess detrimental electronic properties [3]. However, because EBIC is unable to resolve the defect energy levels, many questions are left unanswered. Furthermore, this study, and others like it, employed focused ion beam (FIB) milling to flatten the natively-rough CIGS [3-5], which may run the risk of changing the nature of any near-surface defect structures.

14 SOLAR ENERGY↗
DOE OSTI2020

Significance of a Solid Electrolyte Interphase on Separation of Anode and Cathode Materials from Spent Li-Ion Batteries by Froth Flotation

The separation of electrode active materials from spent Li-ion batteries (LIBs) by froth flotation is challenging due to the changes in surface properties of electrode active materials from cycling as well as the presence of organic binders. In this work, the froth flotation separation of aged anode and cathode composite materials from spent LIBs was systematically investigated after the materials were heat treated. The results show that aged anode and cathode materials from spent LIBs can be well separated from each other after a heating process in air at 400 degrees C and at which some of the PVDF binder remains intact. The underlying mechanism was investigated by X-ray photoelectron spectroscopy (XPS), contact angle measurements, and scanning transmission electron microscopy (STEM) coupled with energy-dispersive X-ray spectroscopy (EDX). The results from the XPS and contact angle measurements show that there is a hydrophilic and oxygen-rich layer on the surface of aged anode materials. This hydrophilic surface, associated with the solid electrolyte interface (SEI) layer, impacts the froth flotation process significantly. The results also show that both the SEI layers and PVDF binder residues on the surface are removed at 400 degrees C for an hour, restoring the hydrophobicity of the anode materials, which, in turn, benefits the separation of anode and cathode materials. The STEM/EDX elemental analysis data confirms that there are 20 nm-thick oxygen-rich SEI layers on the surfaces, which can be removed after a heating process. The present result illustrates the significance of the SEI layers in flotation separation of electrode materials and sheds new lights into the future development of the recycling processes for the separation of anode and cathode composite materials from spent Li-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2026

Chemical and morphological evolution of hybrid conversion coatings in low-Earth orbit space environment

Understanding how protective coatings respond to the harsh low-Earth orbit (LEO) environment is essential for ensuring the safety, longevity, and cost-effectiveness of spacecraft. In particular, identifying environmentally friendly, non-chromate alternatives that can maintain performance under such conditions has both technological and regulatory significance. This study investigates the environmental stability of zirconium-based hybrid conversion coatings with Cu additives (Cu10 and Cu20) applied to cold-rolled steel, tested in the Materials International Space Station Experiment (MISSE) outside the International Space Station (ISS). Chemical and morphological analyses were carried out using a combination of electron microscopy and X-ray spectroscopy techniques, including scanning electron microscopy (SEM), scanning transmission electron microscopy with energy-dispersive X-ray spectroscopy (STEM-EDS), X-ray photoelectron spectroscopy (XPS), and X-ray absorption near-edge structure (XANES) spectroscopy. After exposure outside the ISS, all coatings remained structurally intact, with all exhibiting a uniform Zr-rich matrix and embedded Cu-rich clusters, while a thin Si-rich surface layer developed from interaction with space environments. Depth-resolved XPS showed a layered structure with CuO on the surface, Cu 2 O, and partial Zr(IV) reduction near Cu-rich sites, evidence of Atomic Oxygen (AO)-driven surface oxidation. These results demonstrate that Cu–Zr coatings maintain their chemical integrity and microstructure in harsh space environments, offering a non-chromate alternative for long-term aerospace protection. These insights provide valuable guidance for developing next-generation protective coatings that combine environmental sustainability with the reliability required for future aerospace and orbital applications.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Structural Origins of High MoO 3 Solubility in Peraluminous Borosilicate Glasses

Molybdenum (Mo) imposes strict loading limits in conventional borosilicate nuclear waste glasses due to the tendency of tetrahedral molybdate [MoO 4 ] 2− species to phase-separate and crystallize as alkali molybdates. Here, we demonstrate an unprecedented 13.96 wt % (7.51 mol %) MoO 3 solubility in peraluminous sodium aluminoborosilicate glasses a ∼15× increase over their peralkaline counterparts. Using Raman spectroscopy, multinuclear and dipolarcorrelation magic angle spinning nuclear magnetic resonance (MAS NMR), electron paramagnetic resonance (EPR), and scanning transmission electron microscopy (STEM)-energy dispersive spectroscopy (EDS), we reveal that Nadeficient, low optical basicity conditions stabilize octahedral MoO 6 units, which polymerize into molybdite-like Mo−O clusters dispersed within the glass matrix. These Mo-rich clusters suppress the formation of depolymerized [MoO 4 ] 2− environments typically responsible for Na 2 MoO 4 precipitation and instead promote the formation of Na 2 Mo 2 O 7 as the saturation phase. Concurrently, Mo solubility drives the conversion of AlO 4 − to higher-coordination AlO 5 species, liberating Na + that is subsequently sequestered in molybdate-rich domains. The combined evolution of Mo coordination, modifier redistribution, and network depolymerization provides a mechanistic basis for the markedly enhanced Mo solubility in peraluminous compositions. These findings establish new structural guidelines for designing aluminoborosilicate waste forms with substantially greater capacity to incorporate Mo-rich nuclear waste streams.

Amorphous materials↗
DOE OSTI2021

Revisiting Discharge Mechanism of CF x as a High Energy Density Cathode Material for Lithium Primary Battery

Lithium/fluorinated graphite (Li/CFx) primary batteries show great promise for applications in a wide range of energy storage systems due to their high energy density (>2100 Wh kg –1 ) and low self-discharge rate (<0.5% per year at 25 °C). While the electrochemical performance of the CF x cathode is indeed promising, the discharge reaction mechanism is not thoroughly understood to date. In this article, a multiscale investigation of the CF x discharge mechanism is performed using a novel cathode structure to minimize the carbon and fluorine additives for precise cathode characterizations. Titration gas chromatography, X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, cross-sectional focused ion beam, high-resolution transmission electron microscopy, and scanning transmission electron microscopy with electron energy loss spectroscopy are utilized to investigate this system. Results show no metallic lithium deposition or intercalation during the discharge reaction. Crystalline lithium fluoride particles uniformly distributed with <10 nm sizes into the CF x layers, and carbon with lower sp2 content similar to the hard-carbon structure are the products during discharge. This article deepens the understanding of CF x as a high energy density cathode material and highlights the need for future investigations on primary battery materials to advance performance.

25 ENERGY STORAGE↗
DOE OSTI2023

Elucidating the mechanism underlying the augmented capacity of MoO 2 as an anode material in Li-ion batteries

Transition-metal oxide anode materials have been observed to possess an intriguing surplus of capacity beyond the expected values based on conversion reaction. However, the mechanisms behind this phenomenon have remained contentious and elusive. Here, this study focuses on synthesized nanosized molybdenum dioxide and its electrochemical performance as an anode material for Li-ion batteries. Our findings reveal a substantial increase in capacity upon cycling, achieving approximately 1688 mA h g -1 , nearly double the theoretical capacity, after 700 cycles at a 1C rate. To elucidate the mechanisms underlying this augmented capacity, a comprehensive analysis employing in situ and ex situ X-ray diffraction, X-ray absorption spectroscopy, scanning electron microscopy, and transmission electron microscopy was conducted at various stages of the Li-ion cell cycling. Our results indicate that no conversion reaction occurs during the initial discharge phase, with Li 2 O and Mo remaining undetected. Instead, Li 0.98 MoO 2 is generated upon lithiation. Further materials characterization employing electron energy loss spectroscopy and energy-dispersive X-ray spectroscopy on the cycled electrode suggests the potential formation of a metallic Li-rich layer at the interface of the Li-ion intercalated phase subsequent to the formation of Li 0.98 MoO 2 , contributing to the surplus Li storage. Moreover, electrochemical impedance spectroscopy coupled with ex situ SEM and TEM analyses reveals that alterations in particle size and morphology, along with changes in the solid electrolyte interphase (SEI) resistance, are instrumental in the capacity variation observed upon cycling.

25 ENERGY STORAGE↗
DOE OSTI2020

Role of shell composition and morphology in achieving single-emitter photostability for green-emitting “giant” quantum dots

The use of the varied chemical reactivity of precursors to drive the production of a desired nanocrystal architecture has become a common method to grow thick-shell graded alloy quantum dots (QDs) with robust optical properties. Conclusions on their behavior assume the ideal chemical gradation and uniform particle composition. In this work, advanced analytical electron microscopy (high-resolution scanning transmission electron microscopy coupled with energy dispersive spectroscopy) is used to confirm the nature and extent of compositional gradation and these data are compared with performance behavior obtained from single-nanocrystal spectroscopy to elucidate structure, chemical-composition, and optical-property correlations. In particular, the evolution of the chemical structure and single-nanocrystal luminescence was determined for a time-series of graded-alloy “CdZnSSe/ZnS” core/shell QDs prepared in a single-pot reaction. In a separate step, thick (~6 monolayers) to giant (>14 monolayers) shells of ZnS were added to the alloyed QDs via a successive ionic layer adsorption and reaction (SILAR) process, and the impact of this shell on the optical performance was also assessed. By determining the degree of alloying for each component element on a per-particle basis, we observe that the actual product from the single-pot reaction is less “graded” in Cd and more so in Se than anticipated, with Se extending throughout the structure. The latter suggests much slower Se reaction kinetics than expected or an ability of Se to diffuse away from the initially nucleated core. It was also found that the subsequent growth of thick phase-pure ZnS shells by the SILAR method was required to significantly reduce blinking and photobleaching. However, correlated single-nanocrystal optical characterization and electron microscopy further revealed that these beneficial properties are only achieved if the thick ZnS shell is complete and without large lattice discontinuities. Thus, we identify the necessary structural design features that are required for ideal light emission properties in these green-visible emitting QDs.

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

Dispersible Colloid Facilitated Release of Organic Carbon From Two Contrasting Riparian Sediments

In aqueous systems, including groundwater, nano-colloids (1–100 nm diameter) and small colloids (<450 nm diameter) provide a vast store of surfaces to which organic carbon (OC) can sorb, precluding its normal bioavailability. Because nanomaterials are ubiquitous and abundant throughout Earth systems, it is reasonable that they would play a significant role in biogeochemical cycles. As such, mineral nano-colloids (MNC) and small colloids, formed through mineral weathering and precipitation processes, are both an unaccounted-for reservoir and unquantified vector for transport of OC and nutrients and contaminants within watersheds. Water extractions and leaching experiments were conducted under (1) aerobic (ambient) and (2) anaerobic (environmental chamber) conditions for each of two contrasting riparian sediments from (1) Columbia River, Washington and (2) Tims Branch, South Carolina. Water dispersible colloid-adsorbed OC was as high as 48% of OC for Tims Branch anaerobic batch water extraction and as low as 0% for Columbia River aerobic batch water extractions. Anaerobic leaching from column experiments yielded higher colloid and OC release rates. Transmission electron microscopy with electron dispersive spectroscopy mapping revealed organic carbon associated with aggregations of nano-particulate silicate minerals and Mossbauer identified nano-particulate goethite. This exploratory study demonstrates that mineral facilitated release of OC in riparian sediments is both significant and variable between locations.

Rod, Kenton A.↗
DOE OSTI2025

Calcium is associated with specific soil organic carbon decomposition products at Blodgett Forest Research Center, Georgetown, California as analysed with scanning transmission X-ray microscopy carbon near-edge X-ray absorption fine structure spectroscopy

This data is from the paper calcium is associated with specific soil organic carbon decomposition products, published in SOIL. DOI: https://doi.org/10.5194/soil-11-381-2025, 2025.This file contains CSVs with spectral data and bulk soil data and there is no specific program required to open this data. The data includes Scanning transmission X-ray microscopy carbon near-edge X-ray absorption fine structure spectroscopy. data from the measurement of samples from the Whole-soil Warming project, run by the Belowground Biogeochemistry team at Blodgett Forest Research Center, Georgetown, California run by the University of California, Berkeley. It also includes bulk soil chemical properties. The University of California's Blodgett Forest Research Station (Forest) is situated in the Sierra Nevada foothills (1370 m a.s.l.) near Georgetown, California. The samples were collected from here: 38.912013, -120.661469, https://maps.app.goo.gl/291bCJ1zVqUhgktz6. The Forest soils were characterised as Alfisols, which are equivalent to Dystric Cambisols (IUSS Working Group WRB, 2015), and formed in granitic parent materials, in a temperate climate, under thinned, mixed-coniferous forest (Fig. S3; Gaudinski et al., 2009). With these analyses we aimed to answer the question, is calcium associated with a specific type of organic matter enriched in aromatic and phenolic carbon at the microscale in samples from Blodgett Forest Research Center? and how does this specific type of carbon respond to experiments targetted at removing and adding calcium to the soils, specifically cation exchange and incubation after calcium addition? Abstract from the paper can be found below: Calcium (Ca) may contribute to the preservation of soil organic carbon (SOC) in more ecosystems than previously thought. Here we provide evidence that Ca is co-located with SOC compounds that are enriched in aromatic and phenolic groups, across different acidic soil-types and locations with different ecosystem properties, differing in terms of climate, parent material, soil type, and vegetation. In turn, this co-localised fraction of Ca-SOC is removed through cation-exchange, and the association is then only re-established during decomposition in the presence of Ca (Ca addition incubation). Thus, highlighting a causative link between decomposition and the co-location of Ca with a characteristic fraction of SOC. Decomposition increases the relative proportion of negatively charged functional groups, which can increase the propensity for the association between SOC and Ca, and in turn, this association inhibits dissolved organic carbon export or further decomposition. We propose that this mechanism could be driven by Ca hotspots on the microscale shifting local decomposition processes and thereby explaining the colocation of Ca with SOC of a specific composition across different acidic soil environments. Incorporating this biogeochemical process into Earth System Models could improve our understanding, predictions, and management of carbon dynamics in soils, and account for their response to Ca-rich amendments.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

In Situ Study of Resistive Switching in a Nitride‐Based Memristive Device

Abstract Resistive switching (RS) devices with ultra‐low‐voltage threshold and reliable switching repeatability exhibits great potential applications in energy‐efficient data storage and neuromorphic computing. Understanding switching mechanisms at nanoscale is critical to design RS devices with improved performance. In this work, a lamella memristive device using focused ion beam (FIB) method based on the metal/TiO x /TiN/Si structure device is fabricated. In situ transmission electron microscopy (TEM) and current–voltage ( I–V ) characteristic demonstrate that the lamella device shows a volatile RS behavior with a threshold switching at ≈ ± 0.4 V. In situ scanning transmission electron microscopy (STEM) experiments with electron energy loss spectroscopy (EELS) reveal that the charge carriers such as oxygen vacancies migrate under positive/negative DC bias and modulate Schottky barriers at the top and bottom metal/semiconductor interfaces. The RS mechanism of the lamella device is based on the Schottky barriers modulation and Joule heating assisted electric field triggered thermal runaway (FTTR) occurred at the metal/semiconductor interfaces. The fundamental insights gained from this study presents a perspective on interface‐type RS devices processing and opens up new technological opportunities of fabricating ultra‐low‐energy memristive devices.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Neutral but Impactful: Gallium Cluster-Induced Nanopores from Beam-Blanked Gallium Ion Sources

Neutral atoms originating from liquid metal ion sources are an often-overlooked source of contamination and damage in focused ion beam microscopy. Beyond ions and single atoms, these sources also generate atom clusters. While most studies have investigated charged clusters, here we demonstrate that neutral clusters are also formed. These neutral clusters bypass the electrostatic beam blanking system, allowing them to impinge on samples even when the ion beam is blanked. We investigate this phenomenon using thin (≤20 nm) freestanding membranes of hexagonal boron nitride, silicon, and silicon nitride as targets. Randomly dispersed nanopores that form upon neutral cluster exposure are revealed. The average nanopore diameter is ∼2 nm with a narrow size distribution, suggesting that the atom clusters have a preferred size. Various electron microscopy techniques are used to characterize the nanopores, including high-resolution transmission electron microscopy, multislice ptychography, and electron energy-loss spectroscopy. Finally, we show how electron irradiation in the transmission electron microscope can be used to both remove any amorphous material that may clog the pores and to controllably grow the pores to specific sizes. Tunable nanopores such as these are interesting for nanofluidic applications requiring size-selective membranes.

Byrne, Dana O↗
DOE OSTI2025

Characterization of Gramicidin A in Triblock and Diblock Polymersomes and Hybrid Vesicles via Continuous Wave Electron Paramagnetic Resonance Spectroscopy

Studying membrane proteins in a native environment is crucial to understanding their structural and/or functional studies. Often, widely accepted mimetic systems have limitations that prevent the study of some membrane proteins. Micelles, bicelles, and liposomes are common biomimetic systems but have problems with membrane compatibility, limited lipid composition, and heterogeneity. To overcome these limitations, polymersomes and hybrid vesicles have become popular alternatives. Polymersomes form from amphiphilic triblock or diblock copolymers and are considered more robust than liposomes. Hybrid vesicles are a combination of lipids and block copolymers that form vesicles composed of a mixture of the two. These hybrid vesicles are appealing because they have the native lipid environment of bilayers but also the stability and customizability of polymersomes. Gramicidin A was incorporated into these polymersomes and characterized using continuous wave electron paramagnetic resonance (CW-EPR) and transmission electron microscopy (TEM). EPR spectroscopy is a powerful biophysical technique used to study the structure and dynamic properties of membrane proteins in their native environment. Spectroscopic studies of gramicidin A have been limited to liposomes; in this study, the membrane peptide is studied in both polymersomes and hybrid vesicles using CW-EPR spectroscopy. Lineshape analysis of spin-labeled gramicidin A revealed linewidth broadening, suggesting that the thicker polymersome membranes restrict the motion of the spin label more when compared to liposome membranes. Statement of Significance: Understanding membrane proteins’ structures and functions is critical in the study of many diseases. In order to study them in a native environment, membrane mimetics must be developed that can be suitable for obtaining superior biophysical data quality to characterize structural dynamics while maintaining their native functions and structures. Many currently widely accepted methods have limitations, such as a loss of native structure and function, heterogeneous vesicle formation, restricted lipid types for the vesicle formation for many proteins, and experimental artifacts, which leaves rooms for the development of new biomembrane mimetics. The triblock and diblock polymersomes and hybrid versicles utilized in this study may overcome these limitations and provide the stability and customizability of polymersomes, keeping the biocompatibility and functionality of liposomes for EPR studies of membrane proteins.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Heterostructured nano-catalysts with efficient metal-oxide interfaces unlock high-performance direct methanol protonic ceramic fuel cells

Direct methanol protonic ceramic fuel cells (PCFCs) are attractive due to their low cost, convenient storage, and high volumetric energy density, as well as their suitability for transportation. However, the poor coking tolerance of conventional nickel-based anodes leads to their susceptibility to severe carbon deposition and significant deactivation after long-term exposure to hydrocarbons. Herein, we report a nano-catalyst of Ce 0.6 Ni 0.2 Cu 0.2 O 2 with a heterogeneous structure that is spontaneously reduced into a Ce 0.6 Ni 0.2-x Cu 0.2-x O 2-δ (CeNCO) oxide framework interfaced with a nano NiCu alloy (denoted as NC/CeNCO) under operating conditions, as confirmed by analyses of X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, and transmission electron microscopy. A Ni-BaCe 0.7 Y 0.06 Yb 0.06 Zr 0.06 Hf 0.06 Gd 0.06 O 3-δ anode-supported PCFC employing the NC/CeNCO metal-oxide catalyst achieved a peak power density of 1.11 W cm −2 and operational stability of about 100 h at 700 °C when fueled by 35 % CH 3 OH-15 % H 2 O-50 % N 2 . In conclusion, the enhanced performance and coking resistance are attributed to the efficient interfaces of Ni, Cu, and ceria-based oxide in NC/CeNCO for CH 3 OH reforming, as confirmed by analyses of electrochemical performance and Raman spectroscopy with density functional theory calculations, revealing that these interfaces can enhance CH 3 OH activation and promote efficient OH-mediated carbon removal via COH intermediates.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2024

Development and Application of In Situ Nanocharacterization to Photocatalytic Materials for Solar Fuel Generation

Photocatalytic materials offer an attractive approach for converting solar energy into chemical energy but the performance of the current generation of materials is insufficient to make a technology viable. To address this deficiency, it is necessary to develop a fundamental atomic level understanding of the functioning of such materials so that strategies can be developed to improve performance. This project was undertaken to explore the fundamental structure and properties of photocatalytic materials using atomic resolution imaging and spectroscopy techniques available on advanced transmission electron microscopy. Specifically, there is a need to develop an understanding of how atomic structures/defects and nanoparticle configurations regulate electronic, optical, and catalytic properties to facilitate the design of next generation photocatalysts for solar fuel production. The work focused on fundamental materials information that can be gained from advanced transmission electron microscopy study on novel and existing photocatalytic systems with an emphasis on the hydrogen evolution reaction (HER). Throughout the project, new instrumentation and microscopy characterization tools were developed. Two focus areas were: developing in situ TEM methods and advanced electron energy-loss spectroscopic for nanoscale analysis of catalysts. The work spanned a period of 12 years and for convenience, the report is divided into four phases, approximately corresponding to the four funding periods of the program. Most of the significant results are reported in archival journal publications.

36 MATERIALS SCIENCE↗