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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 127 records · Page 7

Morphological Degradation of Oxygen Evolution Reaction-Electrocatalyzing Nickel Selenides at Industrially Relevant Current Densities

We investigated electrodeposited nanoparticulate nickel selenide (pre)catalysts that transform into nickel oxides/ oxyhydroxides under oxygen evolution reaction conditions in alkaline solutions. Previous studies of this transformation were conducted at lower current densities than those of industrial relevance (≥1 A cm −2 ). We used ultramicroelectrodes (UMEs) to achieve such current densities, benefiting from their small size, ensuring low absolute currents and low ohmic drop but high current densities. Morphological degradation of the catalyst material was only observed at current densities exceeding 1 A cm −2 but not for smaller ones. Using X-ray absorption, Xray photoemission spectroscopy, and X-ray diffraction, we confirmed that the degradation was accompanied by the literature-known transformation of nanoparticulate Ni 3 Se 2 (bulk)/NiSe (surface) into nickel oxyhydroxide. The transformation of the precatalyst goes along with a significant improvement in the charge transfer kinetics observed by decreasing Tafel slopes with ongoing experimental time extracted from cyclic voltammetry (CV) experiments and electrochemical impedance spectroscopy (EIS) in the high-frequency range. However, these kinetic improvements are accompanied by limitations in mass transport concluded from decreasing current responses at high overpotentials in CVs and increasing impedance in the low-frequency range of the EIS spectra after extended CV cycling. These mass transport limitations originated from morphological degradations at the UME exceeding 1 A cm −2 which we proved by applying identical location scanning electron microscopy. This has not been reported in studies that have been limited to lower current densities before. Our findings showcase how UMEs can be used to study (pre)catalysts (herein nickel selenides) under current densities of industrial relevance in the absence of ohmic drop-related ambiguities, combined with in-depth materials characterization studies, e.g., identical location microscopy and advanced spectroscopic methods. This approach enables direct evaluation and comparison of catalyst materials and thus demonstrates how to overcome long-standing limitations of electrocatalyst design and testing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

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↗

Unveiling Feedstock Variability: Insights into Corn Stover Conversion - Part I: Physicochemical Properties and Self-Degradation

Transforming agricultural waste into biofuels and bioproducts is crucial to advancing a low-carbon bioeconomy. However, the inherent variability in the composition and quality introduces uncertainties in the conversion efficiency and poses challenges in process development. Through integrating a high-throughput conversion system, material characterization techniques, and advanced data analysis tools, this study investigates the variability of corn stover and its subsequent impacts on carbohydrate conversion. The findings reveal that indoor storage substantially reduces the moisture and ash content and soil contamination, while other properties remain largely unchanged. Self-degradation due to microbial activity during storage decreases the carbohydrate content of corn stover but enhances glucose and xylose yields. A negative correlation is observed between sugar yields and lignin content across samples with varying ash and moisture content. The inhibitory effect of lignin diminishes in self-degraded samples likely due to the disrupted cell wall structure. Although self-degradation slightly increases cellulose crystallinity, no strong correlation was observed between the crystallinity and sugar yield. Hot water pretreatment under mild conditions effectively mitigates inherent variability, consistently improving the sugar yield from corn stover by up to 50%. By elucidating the feedstock variability and its impact on convertibility, these findings offer valuable insights into appropriate feedstock handling and management, highlighting potential strategies to address variability challenges.

09 BIOMASS FUELS↗

Spatial Heterogenous Redox Couples Degradation in Sodium-Ion Battery Cathode Materials and the Mitigation of Voltage Fade by Blocking Oxygen Release

The use of anionic redox has become a new paradigm for improving the energy density of rechargeable batteries, which is essential for improving the market competitiveness of sodium-ion batteries. However, issues such as voltage attenuation and cycling stability degradation persist in layered oxide anion redox cathode materials. Here, in this study, we systematically investigate the classic Na-ion cathode material Na 0.6 Li 0.2 Mn 0.8 O 2 , and the primary causes of voltage decay are identified as the activation of cations and the reduction in anion redox activity. In addition, the activation of cations is closely associated with anion reactions. Through the application of sophisticated multiscale synchrotron absorption spectroscopy and imaging techniques, we have identified a pronounced pattern of spatially dependent degradation in the evolution of redox couples, which is more evident from the material’s surface to its core. With this understanding, we introduced a surface fluorination approach that modulates the local chemical coordination environment. This strategy increases the formation energy of surface oxygen vacancies and locks transition metals oxide state. Consequently, it enables more reversible anionic redox reactions, which block the spatial progression of degradation and mitigates voltage decay.

25 ENERGY STORAGE↗

Healing Gradient Degradation in Nb3Sn SRF Cavities Using a Recoating Method

Despite having advantageous superconducting properties, Nb3Sn superconducting radiofrequency (SRF) cavities still have practical challenges compared to Nb SRF cavities due to the brittle nature of Nb3Sn. Performance degradation can occur when a Nb3Sn SRF cavity experiences mechanical stresses such as during handling and tuning of the cavity. In this study, we present a potential treatment for SRF cavities that have experienced stress induced performance degradation that involves a recoating procedure. The degraded cavity is coated with a small amount of Sn using a single step vapor-diffusion methodology. Using this approach we can recover a significant portion of the lost performance of a Nb3Sn SRF cavity.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Correlating hot-electron preheat from the two-plasmon decay instability to $ρR$ degradation for direct-drive implosions on OMEGA

Focused experiments were performed with the goal of isolating the impact of hot-electron preheat on compression in deuterium–tritium (DT) layered, direct-drive implosions on OMEGA. Preheat from the hot-electrons generated by two-plasmon–decay (TPD) activity was varied through the incident laser intensity, with the total preheat energy deposited into unablated DT fuel being inferred using hard x-ray measurements. Results show a clear correlation between the inferred preheat levels and $ρR$ degradation that is consistent with a derived, 1D preheat model. A fit to the results also provides an estimated range of $ρR$ degradation from non-preheat sources for the adiabat ≈5 implosions used in this study. A follow-up study using targets containing Si-doped (5.5%) CH ablators (CHSi) demonstrated results consistent with mid-Z dopants mitigating TPD activity by showing these targets had almost no $ρR$ degradation as the laser intensity was increased up to levels previously considered damaging.

Doping↗

The DYRKP1 kinase regulates cell wall degradation in Chlamydomonas by inducing matrix metalloproteinase expression

Abstract The cell wall of plants and algae is an important cell structure that protects cells from changes in the external physical and chemical environment. This extracellular matrix, composed of polysaccharides and glycoproteins, must be constantly remodeled throughout the life cycle. However, compared to matrix polysaccharides, little is known about the mechanisms regulating the formation and degradation of matrix glycoproteins. We report here that a plant kinase belonging to the dual-specificity tyrosine phosphorylation-regulated kinase (DYRKP1) family present in all eukaryotes regulates cell wall degradation after mitosis of Chlamydomonas reinhardtii by inducing the expression of matrix metalloproteinases. Without DYRKP1, daughter cells cannot disassemble parental cell walls and remain trapped inside for more than 10 days. On the other hand, the dual-specificity tyrosine phosphorylation-regulated kinase complementation lines show normal degradation of the parental cell wall. Transcriptomic and proteomic analyses indicate a marked downregulation of MMP gene expression and accumulation, respectively, in the dyrkp1 mutants. The mutants deficient in matrix metalloproteinases retain palmelloid structures for a longer time than the background strain, like dyrkp1 mutants. Our findings show that dual-specificity tyrosine phosphorylation-regulated kinase, by ensuring timely MMP expression, enables the successful execution of the cell cycle. Altogether, this study provides insight into the life cycle regulation in plants and algae.

Kim, Minjae (ORCID:0000000223561295)↗

Genomics and physiology of Catenibacillus, human gut bacteria capable of polyphenol C-deglycosylation and flavonoid degradation

The genusCatenibacillus(familyLachnospiraceae, phylumBacillota) includes only one cultivated species so far,Catenibacillus scindens,isolated from human faeces and capable of deglycosylating dietary polyphenols and degrading flavonoid aglycones. Another human intestinalCatenibacillusstrain not taxonomically resolved at that time was recently genome-sequenced. We analysed the genome of this novel isolate, designatedCatenibacillus decagia, and showed its ability to deglycosylateC-coupled flavone and xanthone glucosides andO-coupled flavonoid glycosides. Most of the resulting aglycones were further degraded to the corresponding phenolic acids. Including the recently sequenced genome ofC. scindensand ten faecal metagenome-assembled genomes assigned to the genusCatenibacillus, we performed a comparative genome analysis and searched for genes encoding potentialC-glycosidases and other polyphenol-converting enzymes. According to genome data and physiological characterization, the core metabolism ofCatenibacillusstrains is based on a fermentative lifestyle with butyrate production and hydrogen evolution. BothC. scindensandC. decagiaencode a flavonoidO-glycosidase, a flavone reductase, a flavanone/flavanonol-cleaving reductase and a phloretin hydrolase. Several gene clusters encode enzymes similar to those of the flavonoidC-deglycosylation system ofDoreastrain PUE (DgpBC), while separately located genes encode putative polyphenol-glucoside oxidases (DgpA) required forC-deglycosylation. The diversity ofdgpAanddgpBCgene clusters might explain the broadC-glycoside substrate spectrum ofC. scindensandC. decagia. The otherCatenibacillusgenomes encode only a few potential flavonoid-converting enzymes. Our results indicate that severalCatenibacillusspecies are well-equipped to deglycosylate and degrade dietary plant polyphenols and might inhabit a corresponding, specific niche in the gut.

Genetics & Heredity↗

In-Situ Luminescence Imaging of Perovskite Solar Cells Demonstrates Increasing Spatial Nonuniformity Upon Light-Soaking Degradation

In this work we investigate degradation rates of triplecation mixed-halide perovskite p-i-n solar cells. We present an accelerated stress testing procedure using periodic blue light-soaking at elevated temperatures until devices reach ~80% of their initial efficiency. We track light-induced degradation via in-situ: photoluminescence (PL), current-voltage (I-V) curves, and transient photovoltage. Devices underwent 165 hours of light bias at 65degrees C. Results suggest that spatial uniformity in PL intensity decreases as device degradation increases. This investigation lays the groundwork to address the current gap in understanding the interplay between device performance and the evolution of macroscopic features in perovskite solar cells. Thus, we believe spatial characterization techniques will play a crucial role in the commercialization of perovskite solar cells.

imaging↗

Degradation of Fuel Cell Membrane Electrode Assemblies from Buses Operated More than 25,000 h

This study investigates the performance losses and degradation of proton-exchange-membrane fuel-cell stacks taken from the Alameda Contra Costa Transit District (AC Transit) bus system (Alameda and Contra Costa counties, California, United States) that were operated for over 25,000 h. Here, we focus on the origin of differences in electrochemical performance between beginning-of-life (BOL) and end-of-life states as well as diagnostic data acquired during the lifetime of the buses. In doing so, we employ in- and ex- situ characterization methods such as polarization curves, electrochemical impedance spectroscopy, electron microscopy, and X-ray characterization. Uniform degradation of the catalyst layer including Pt agglomeration/migration and electrode thinning was observed in all of the post-teardown measurements compared to BOL materials resulting from years of field operation. Despite these changes, the measured post-teardown performance suggests a sufficient output for the expected load, which indicate factors other than degradation of the membrane-electrode assemblies (MEAs) are likely responsible for the decommissioning of the stacks. The findings indicate that these MEA materials can enable long lifetime in fuel-cell vehicles, if the MEAs are not subjected to adverse operating conditions. The results also highlight the need for more in-vehicle diagnostics to maximize the lifetime of fuel cell vehicle (FCV) powerplants.

25 ENERGY STORAGE↗

Temporal and spatial resolution of magnetosome degradation at the subcellular level in a 3D lung carcinoma model

Magnetic nanoparticles offer many exciting possibilities in biomedicine, from cell imaging to cancer treatment. One of the currently researched nanoparticles are magnetosomes, magnetite nanoparticles of high chemical purity synthesized by magnetotactic bacteria. Despite their therapeutic potential, very little is known about their degradation in human cells, and even less so of their degradation within tumours. In an effort to explore the potential of magnetosomes for cancer treatment, we have explored their degradation process in a 3D human lung carcinoma model at the subcellular level and with nanometre scale resolution. We have used state of the art hard X-ray probes (nano-XANES and nano-XRF), which allow for identification of distinct iron phases in each region of the cell. Our results reveal the progression of magnetite oxidation to maghemite within magnetosomes, and the biosynthesis of magnetite and ferrihydrite by ferritin.

36 MATERIALS SCIENCE↗

Optimization of Solid Oxide Electrolysis Cell Systems Accounting for Long-Term Performance and Health Degradation

This study focuses on optimizing solid oxide electrolysis cell (SOEC) systems for efficient and durable long-term hydrogen (H2) production. While the elevated operating temperatures of SOECs offer advantages in terms of efficiency, they also lead to chemical degradation, which shortens cell lifespan. To address this challenge, dynamic degradation models are coupled with a steady-state, two-dimensional, non-isothermal SOEC model and steady-state auxiliary balance of plant equipment models, within the IDAES modeling and optimization framework. A quasi-steady state approach is presented to reduce model size and computational complexity. Long-term dynamic simulations at constant H2 production rate illustrate the thermal effects of chemical degradation. Dynamic optimization is used to minimize the lifetime cost of H2 production, accounting for SOEC replacement, operating, and energy expenses. Several optimized operating profiles are compared by calculating the Levelized Cost of Hydrogen (LCOH).

Giridhar, Nishant↗

Advanced Sensors for In-Situ Amine Degradation Monitoring in Post-Combustion Carbon Capture

In order to improve the long-term performance of post-combustion carbon capture technologies, improvements to the detection of solvent degradation or reduction in CO2 capture efficiency are necessary. A pair of sensors were deployed to the National Carbon Capture Center’s (NCCC) to monitor CO2 capture and solvent degradation. The CO2 sensors were located to measure before capture and after capture concentrations of CO2 to measure the capture efficiency of the solvent system. Amine degradation sensors were located at four locations along the main solvent lines corresponding to CO2 loading and temperature: hot rich, cold rich, hot lean, and cold lean. Experimental results from laboratory tests using the sensors are shown, along with prototype designs that were deployed to the field site.

Brister, Matthew↗

Optimal Operation of Solid-Oxide Electrolysis Cell Systems Considering Synergistic Chemical and Physical Degradation

This poster summarizes work on synergistic degradation of Solid-Oxide Cells under physical and chemical degradation. We present operational insights that extend the useful life of SOCs while maintaining high efficiencies and economic viability. We also provide insights on how often the SOC must be replaced to ensure the reliability of the process. All these decisions are made through a dynamic optimization framework that utilizes new models for degradation that were developed as a part of the IDAES project.

Giridhar, Nishant↗

Characterization of Performance Degradation Mechanisms in Low-Cost High Throughput DI-O3 Layer for Passivated Contact Silicon Solar Cells

Characterization and mitigating performance limiting defects in Silicon (Si) PV is one of key areas to be addressed to improve PV hardware costs and energy yield in order to lower the levelized cost of energy (LCOE) of installed PV cost to $0.02/kWh. As Si PV cells efficiencies have surpassed 22% and approaching 23%, the recombination at the metal contacts have become the focus point to be addressed. Passivated contact technologies—having a heterojunction with a band-gap larger than silicon between the metal and silicon—have emerged as a great potential for future highand ultrahigh-efficiency solar cells, as it concurrently reduces recombination and increases carrier selectivity, by incorporating thin films within the contact structure. Passivated contact Si solar cell technologies use a wide variety of tunnel layers—playing a crucial role to passivate metal contacts and tunnel charge carriers—including stoichiometric silicon oxide (SiO 2 ) grown by thermal oxidation and Low-Pressure Chemical Vapor Deposition (LPCVD) technique and silicon oxide (SiO x ) by hot nitric acid. However, thorough investigations on understanding the failure and performance degradation mechanisms associated with tunnel layers are still limited to date. Unlocking those degradation characteristics in crucial tunnel layers could improve the reliability and energy yield of passivated contact Si solar cells. Besides, the technique of growing aforementioned tunneling layers are low throughput, and requires high temperature processes and/or a vacuum environment. In this project, we investigated the performance degradation mechanisms of a low-cost high-throughput ozonated oxide (DI-O 3 ) tunnel layer for the passivated contact Si solar cells.

14 SOLAR ENERGY↗

Electrospun Nanofiber Dopped with TiO2 and Carbon Quantum Dots for the Photocatalytic Degradation of Antibiotics

Novel photocatalysts were synthesized through the association of carbon quantum dots (CQDs) with commercial (P25) titanium dioxide (TiO2) by sonication. The resulting TiO2/CQDs composite was then incorporated into the polyamide 66 (PA66) biopolymer nanofibers using the electrospinning technique, considering a composite nanoparticles-to-polymer ratio of 1:2 in the electrospinning precursor solution. The produced nanofibers presented suitable morphology and were tested for the photocatalytic degradation under simulated solar radiation of 10 mg L−1 of amoxicillin (AMX) and sulfadiazine (SDZ), in phosphate buffer solution (pH 8.06) and river water, using 1.5 g L−1 of photocatalyst. The presence of the photocatalyst increased the removal of AMX in phosphate buffer solution by 30 times, reducing the AMX degradation half-life time from 62 ± 1 h (without catalyst) to 1.98 ± 0.06 h. Moreover, SDZ degradation half-life time in phosphate buffer solution was reduced from 5.4 ± 0.1 h (without catalyst) to 1.87 ± 0.05 h in the presence of the photocatalyst. Furthermore, the PA66/TiO2/CQDs were also efficient in river water samples and maintained their performance in at least three cycles of SDZ photodegradation in river water. The presented results evidence that the produced photocatalyst can be a promising and sustainable solution for antibiotics’ efficient removal from water.

Silva, Valentina (ORCID:0000000285394787)↗

Optimization of Solid Oxide Electrolysis Cell Systems Accounting for Long-Term Performance and Health Degradation

This study focuses on optimizing solid oxide electrolysis cell (SOEC) systems for efficient and durable long-term hydrogen (H2) production. While the elevated operating temperatures of SOECs offer advantages in terms of efficiency, they also lead to chemical degradation, which shortens cell lifespan. To address this challenge, dynamic degradation models are coupled with a steady-state, two-dimensional, non-isothermal SOEC model and steady-state auxiliary balance of plant equipment models, within the IDAES modeling and optimization framework. A quasi-steady state approach is presented to reduce model size and computational complexity. Long-term dynamic simulations at constant H2 production rate illustrate the thermal effects of chemical degradation. Dynamic optimization is used to minimize the lifetime cost of H2 production, accounting for SOEC replacement, operating, and energy expenses. Several optimized operating profiles are compared by calculating the Levelized Cost of Hydrogen (LCOH).

Giridhar, Nishant↗

Targeted protein degradation systems to enhance Wnt signaling

Molecules that facilitate targeted protein degradation (TPD) offer great promise as novel therapeutics. The human hepatic lectin asialoglycoprotein receptor (ASGR) is selectively expressed on hepatocytes. We have previously engineered an anti-ASGR1 antibody-mutant RSPO2 (RSPO2RA) fusion protein (called SWEETS) to drive tissue-specific degradation of ZNRF3/RNF43 E3 ubiquitin ligases, which achieved hepatocyte-specific enhanced Wnt signaling, proliferation, and restored liver function in mouse models, and an antibody–RSPO2RA fusion molecule is currently in human clinical trials. In the current study, we identified two new ASGR1- and ASGR1/2-specific antibodies, 8M24 and 8G8. High-resolution crystal structures of ASGR1:8M24 and ASGR2:8G8 complexes revealed that these antibodies bind to distinct epitopes on opposing sides of ASGR, away from the substrate-binding site. Both antibodies enhanced Wnt activity when assembled as SWEETS molecules with RSPO2RA through specific effects sequestering E3 ligases. In addition, 8M24-RSPO2RA and 8G8-RSPO2RA efficiently downregulate ASGR1 through TPD mechanisms. These results demonstrate the possibility of combining different therapeutic effects and degradation mechanisms in a single molecule.

59 BASIC BIOLOGICAL SCIENCES↗