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At least 523 records · Page 29

Hydroxylation and Cation Segregation in (La 0.5 Sr 0.5 )FeO 3-$δ$ Electrodes

Simultaneously achieving high activity and stability is the primary challenge when engineering (electro)catalysts. Transition metal perovskite oxides are employed as air electrodes for solid-oxide fuel cells and electrolyzers. However, degradation of oxygen exchange kinetics at the solid–gas interface, often linked to alkaline-earth cation segregation and precipitation, limits widespread commercialization. Here, we systematically investigated the surface degradation mechanism induced by gas-phase impurities in La 0.5 Sr 0.5 )FeO 3-$δ$ (LSF55) thin-film electrodes by varying the concentration of H 2 O, SO 2 , and CO 2 . Degradation of the area-specific resistance in ambient and humidified synthetic air is significantly greater than in dry ambient and dry synthetic air, pointing to the importance of water vapor. Time-resolved, in situ ambient pressure X-ray photoelectron spectroscopy performed in O 2 showed that nonbulk Sr is present on the surface before the exposure to water vapor. Upon introduction of water vapor, neither additional Sr segregation nor precipitation driven by water vapor is a necessary condition for degradation. Rather, hydroxylation of the surface induces irreversible and significant degradation. At the same time, we show that Sr migration driven by water vapor is partially reversible. These fundamental insights can be used for the rational design of electrodes with improved catalytic stability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Photochemical micromotor of eccentric core in isotropic hollow shell exhibiting multimodal motion behavior

Adaptive motion behavior in response to different environmental stimuli is ubiquitous in biology and enables creatures to achieve a diversity of complex tasks, but not typically observed in synthetic systems. In this report we propose a design of chemically-powered micromotors actively performing multimodal motion behaviors with the external stimulus changing. They have isotropic outer surfaces but inherent inner mass asymmetry, such as eccentric core-in-hollow shell TiO 2 (E-TiO 2 ) microspheres. Their motion behavior can be spontaneously transformed among random Brownian propulsion (stochastic walk), negative phototaxis (moving against incident light), and negative photogravitaxis (moving against gravity) when the light intensity, illumination direction, or fuel concentration change. At a low light intensity and/or low H 2 O 2 fuel concentration, the E-TiO 2 micromotors perform directional movement away from light based on the dominated diffusiophoresis by the photocatalytic reaction over the isotropic shell. With the increase of light intensity or fuel concentration, there are more and more photons or fuels to reach the eccentric core and the contribution of the photocatalytic reaction over it to the diffusiophoresis gradually becomes dominant. In this case, the E-TiO 2 micromotors perform stochastic walks near the substrate due to their Brownian random rotational reorientations. The micromotors are single component, have low density, and can be synthesized in a large scale and at a low cost. This work will facilitate the development of multifunctional micro/nanomotors with varying behaviors and functions depending on environmental cues, e.g., enabling efficient search and delivery operations.

36 MATERIALS SCIENCE↗

Gas-phase microactuation using kinetically controlled surface states of ultrathin catalytic sheets

Biological systems convert chemical energy into mechanical work by using protein catalysts that assume kinetically controlled conformational states. Synthetic chemomechanical systems using chemical catalysis have been reported, but they are slow, require high temperatures to operate, or indirectly perform work by harnessing reaction products in liquids (e.g., heat or protons). Here, we introduce a bioinspired chemical strategy for gas-phase chemomechanical transduction that sequences the elementary steps of catalytic reactions on ultrathin (<10 nm) platinum sheets to generate surface stresses that directly drive microactuation (bending radii of 700 nm) at ambient conditions (T = 20 °C; P total = 1 atm). When fueled by hydrogen gas and either oxygen or ozone gas, we show how kinetically controlled surface states of the catalyst can be exploited to achieve fast actuation (600 ms/cycle) at 20 °C. Finally, we also show that the approach can integrate photochemically controlled reactions and can be used to drive the reconfiguration of microhinges and complex origami- and kirigami-based microstructures.

42 ENGINEERING↗

Anomaly Detection for Online Monitoring of Thermocouple Sensors in the Advanced Test Reactor

This study explores data-driven anomaly detection methods to analyze sensor fail- ures in the Advanced Gas Reactor (AGR) nuclear fuel irradiation experiments. Specifically, we examine failures of thermocouples (TCs), which are critical for mon- itoring and controlling in-reactor temperatures during operation. Failures were pri- marily observed during abrupt power transitions and manifested as sensor drop-outs, drifts, or unexplained behavior. We applied three time-series analysis techniques— rolling mean smoothing, matrix profile, and vector auto-regression (VAR)—to de- tect anomalies in TC data prior to failure events. The rolling mean method effec- tively highlighted deviations aligned with reported failures, while the matrix profile provided partial early warning but sometimes flagged normal fluctuations during power-down periods. VAR shows potential in capturing multivariate dependencies but requires further calibration. A rare case of TC drift was also documented, which did not result in failure, underscoring the challenge of building predictive models with sparse positive examples. Our findings demonstrate that traditional statistical tools can aid anomaly detection but have limited predictive power without richer training data. We propose future directions including synthetic data generation, real- time surrogate modeling, and multi-modal feature integration. This work provides a foundation for applying robust anomaly detection frameworks to mission-critical sensor systems in experimental settings.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Nitrogen management during decarbonization

Decarbonization is crucial to combat climate change. However, some decarbonization strategies could profoundly impact the nitrogen cycle. Here, in this Review, we explore the nitrogen requirements of five major decarbonization strategies to reveal the complex interconnections between the carbon and nitrogen cycles and identify opportunities to enhance their mutually sustainable management. Some decarbonization strategies require substantial new nitrogen production, potentially leading to increased nutrient pollution and exacerbation of eutrophication in aquatic systems. For example, the strategy of substituting 44% of fossil fuels used in marine shipping with ammonia-based fuels could reduce CO 2 emissions by up to 0.38 Gt CO 2 -eq yr -1 but would require a corresponding increase in new nitrogen synthesis of 212 Tg N yr -1 . Similarly, using biofuels to achieve 0.7 ± 0.3 Gt CO 2 -eq yr -1 mitigation would require new nitrogen inputs to croplands of 21–42 Tg N yr -1 . To avoid increasing nitrogen losses and exacerbating eutrophication, decarbonization efforts should be designed to provide carbon–nitrogen co-benefits. Reducing the use of carbon-intensive synthetic nitrogen fertilizer is one example that can simultaneously reduce both nitrogen inputs by 14 Tg N yr -1 and CO 2 emissions by 0.04 (0.03–0.06) Gt CO 2 -eq yr -1 . Future research should guide decarbonization efforts to mitigate eutrophication and enhance nitrogen use efficiency in agriculture, food and energy systems.

54 ENVIRONMENTAL SCIENCES↗

Prospective Life Cycle Assessment of Synthetic Graphite Manufactured via Electrochemical Graphitization

Lithium-ion batteries (LIBs) are expected to play a crucial role in meeting many of the clean energy-related goals. Due to its electrical properties such as good conductance, chemical inertness, and corrosion resistance, graphite is a very popular anode for LIBs. Traditional methods of producing battery-grade graphite (high purity >99%) include processing naturally mined graphite or manufacturing synthetic graphite via the Acheson process, which converts soft amorphous carbons such as petroleum coke into graphite by subjecting it to high temperature (up to 3000 °C) for prolonged periods of times (3–5 days). However, due to a lack of abundant high purity natural graphite sources, synthetic graphite is the preferred choice for many LIBs. A new synthetic electrochemical graphitization method that subjects the amorphous carbon precursor submerged in a molten salt mixture to a constant cathodic polarization (against a graphitic anode) has been discovered that has significantly lower graphitization temperatures (~800 °C) and reduced graphitization time (3–6 h). Furthermore, the method can accept a higher variety of carbon precursors compared to the Acheson process. A prospective life cycle assessment (LCA) is conducted on this new method and compared against the traditional processes. The laboratory-scale demonstration of the method is used to build an inventory, which through various assumptions is scaled up to a commercial scale. An additional scenario is also considered with a biomass-derived carbon precursor for the graphite. The results from the LCA show that while the laboratory scale process is similar to the Acheson process and natural flake graphite in terms of impact, the scaled-up process is drastically better than the Acheson process in all environmental categories. Using a coconut shell-derived biomass precursor has a higher impact due to its manufacturing in Indonesia, as the Indonesian energy grid is highly fossil fuel dependent. Therefore, the biomass carbon may have a higher impact than petroleum coke dependent on the location of production of biomass-derived carbon black. The LCA has identified the molten salt—CaCl 2 —as a potential hotspot and suggests other salts should be considered. Accordingly, the new method shows promise in this early stage LCA in improving the environmental performance of graphite (and by relation LIBs) and therefore needs to be explored more in terms of its commercial viability.

25 ENERGY STORAGE↗

Phenotypic and genomic characterization of Methanothermobacter wolfeii strain BSEL, a CO 2 -capturing archaeon with minimal nutrient requirements

A new variant of Methanothermobacter wolfeii was isolated from an anaerobic digester using enrichment cultivation in anaerobic conditions. Here, the new isolate was taxonomically identified via 16S rRNA gene sequencing and tagged as M. wolfeii BSEL. The whole genome of the new variant was sequenced and de novo assembled. Genomic variations between the BSEL strain and the type strain were discovered, suggesting evolutionary adaptations of the BSEL strain that conferred advantages while growing under a low concentration of nutrients. M. wolfeii BSEL displayed the highest specific growth rate ever reported for the wolfeii species (0.27 ± 0.03 h –1 ) using carbon dioxide (CO 2 ) as unique carbon source and hydrogen (H 2 ) as electron donor. M. wolfeii BSEL grew at this rate in an environment with ammonium (NH 4 + ) as sole nitrogen source. The minerals content required to cultivate the BSEL strain was relatively low and resembled the ionic background of tap water without mineral supplements. Optimum growth rate for the new isolate was observed at 64°C and pH 8.3. In this work, it was shown that wastewater from a wastewater treatment facility can be used as a low-cost alternative medium to cultivate M. wolfeii BSEL. Continuous gas fermentation fed with a synthetic biogas mimic along with H 2 in a bubble column bioreactor using M. wolfeii BSEL as biocatalyst resulted in a CO 2 conversion efficiency of 97% and a final methane (CH 4 ) titer of 98.5%v, demonstrating the ability of the new strain for upgrading biogas to renewable natural gas.

09 BIOMASS FUELS↗

Sol–gel synthesis of iodosodalite precursors and subsequent consolidation with a glass binder made from oxides and sol–gel routes

Radioiodine accumulates in aqueous solutions and off-gas streams during nuclear fuel reprocessing due to its solubility in aqueous solutions and volatility, respectively. Additionally, radioiodine is highly mobile in geological environments and iodine-129 has been found to be one of the largest long-term contributors to chronic dose to humans in scenarios of radionuclide migration from geological repositories. Most of the radioiodine can be captured during fuel reprocessing in off-gas streams using solid sorbents and scrubbing solutions. Once iodine is captured, it must be stored in a durable form for eventual disposal. Iodosodalite has been investigated as a waste form for radioiodine, however these synthesis processes typically result in mixed products and iodine volatilization during consolidation. Therefore, this paper proposes a novel approach to synthesizing iodosodalite utilizing a sol-gel method. This method was chosen to lower processing temperatures and improve product yield. Preliminary experiments conducted to determine the viability of this synthetic method are presented. Additionally, consolidation of sol-gel derived iodosodalite with a glass-binder was explored using three different methods: 1) incorporating the glass-binder during gel preparation using alkoxide precursors; 2) separately preparing the glass binder using a sol-gel method; and 3) separately preparing the glass-binder using a melt-quench technique. Glass-bonded iodosodalite was successfully synthesized using these novel sol-gel approaches.

36 MATERIALS SCIENCE↗

Computational Investigation of MAX as Intercalation Host for Rechargeable Aluminum‐Ion Battery

Abstract Layered carbides and their analogs with MAX phase (general formula AM n+1 X n ) have emerged as promising candidates for energy storage and conversion applications. One frontier for energy storage is using MAX as an Al‐ion intercalation electrode. Given that many MAXs have Al as the A sites, the structure can potentially serve as a stable host for Al intercalation. Here in this work, 425 ternary MAX Al‐ion battery electrodes are computationally enumerated. Specifically, first principal phase diagram calculations are performed on the combinatorial space of 17 types of typical transition metals, five types of anions (C, N, B, Si, and P), three types of stoichiometries (n = 1, 2, and 3) and two types of layered stackings (α and β). Among all the ternary MAX materials, 44 candidates show reasonable synthetic accessibility, and six with extraordinary performance are predicted to be promising Al‐ion battery electrodes. With the phase stability, and electrochemical performance (average voltage, theoretical capacity, energy density, and Al diffusion barrier), the work provides a comprehensive computational assessment of the great opportunities behind MAX‐based Al‐ion batteries.

Chemistry↗

Multigene engineering in plants: Technologies, applications, and future prospects

The emerging bioeconomy presents a promising solution to both economic and environmental challenges. Within the bioeconomy, plants serve as a renewable, sustainable, and cost-effective source of foods, fuels, chemicals, and materials. However, traditional breeding and single-gene engineering approaches fall short in addressing complex traits (e.g., drought tolerance, disease resistance, yield, nutrient use efficiency) which are controlled by multiple genes. The complexity of plant biology often necessitates the use of multigene engineering (MGE), which involves simultaneous ectopic expression, up/down-regulation, or editing of multiple genes, to enhance plant traits relevant to the bioeconomy. These genes may be associated with distinct traits or function as components of specific metabolic and regulatory pathways. This review summarizes current technologies for MGE within the synthetic biology-driven Design-Build-Test-Learn (DBTL) framework, detailing its four key stages: Design – gene construct development; Build – DNA assembly and plant transformation; Test – the molecular, biochemical, and physiological characterization of engineered plants; and Learn – computational modeling to refine, multiplex and iterate the process. Despite good progress in the applications of MGE in biofortification, metabolic engineering, and stress resilience, challenges remain in construct stability, coordinated gene expression, and regulatory predictability. We identified optimization paths and future directions to accelerate MGE deployment in sustainable agriculture, with possible societal benefits including reduced production costs, increased yield, and improved food and nutritional security.

AI-aided plant engineering↗

Simultaneous quantification of uranium( VI ), samarium, nitric acid, and temperature with combined ensemble learning, laser fluorescence, and Raman scattering for real-time monitoring

In this work, laser-induced fluorescence spectroscopy (LIFS), Raman spectroscopy, and a stacked regression ensemble was developed for near real-time quantification of uranium(VI) (1–100 μg mL –1 ), samarium (0–200 μg mL –1 ) and nitric acid (0.1–4 M) with varying temperature (20 °C–45 °C). LIFS applications range from fundamental lab-scale studies to real-time process monitoring at industrial levels, such as nuclear reprocessing applications, provided the phenomena affecting the fluorescence spectrum are accounted for (e.g., absorption, quenching, complexation). Multiple chemometric models were examined and compared to a more traditional multivariate regression approach called partial least squares (PLS). Results obtained on synthetic samples selected using D-optimal experimental design indicated that a stacked regression method, which included ridge regression, random forest, PLS, and an eXtreme gradient boost algorithm, successfully measured uranium(VI) concentrations directly in nitric acid without measuring luminescence lifetimes or standard addition. The top model resulted in percent root-mean-square error of prediction values of 5.2, 1.9, 3.0, and 2.3% for U(VI), Sm 3+ , HNO 3 , and temperature, respectively. The approach may be useful for quantifying fluorescent fission products (e.g., Sm 3+ ) to provide information on burnup of irradiated nuclear fuel. This novel framework reinforces the applicability of LIFS for real-time applications in nuclear fuel cycle applications.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Inferring performance metrics for laser direct drive experiments on OMEGA

Quantifying performance improvements on the OMEGA laser facility requires robust inference of established no-alpha performance metrics, which requires, at minimum, a model to infer the shocked fuel mass and pressure of the confined fusion plasma. In this work, we describe the methodology used to infer performance metrics on OMEGA and present the current state-of-the art model used to infer these metrics from OMEGA experiments. In particular, since neutron images of cryogenic implosions are not available on OMEGA at present, we present how x-ray sizes are determined on OMEGA using a Gaussian Process regression model and how the neutron production region's size is inferred from them. As a result, we end by benchmarking the model using synthetic data and 1-D LILAC simulations and test its experimental self-consistency across available x-ray diagnostic channels.

Gopalaswamy, V. [Laboratory for Laser Energetics, ↗

Multivariate Bayesian Optimization of CoO Nanoparticles for CO 2 Hydrogenation Catalysis

The hydrogenation of CO 2 holds promise for transforming the production of renewable fuels and chemicals. However, the challenge lies in developing robust and selective catalysts for this process. Transition metal oxide catalysts, particularly cobalt oxide, have shown potential for CO 2 hydrogenation, with performance heavily reliant on crystal phase and morphology. Achieving precise control over these catalyst attributes through colloidal nanoparticle synthesis could pave the way for catalyst and process advancement. Yet, navigating the complexities of colloidal nanoparticle syntheses, governed by numerous input variables, poses a significant challenge in systematically controlling resultant catalyst features. We present a multivariate Bayesian optimization, coupled with a data-driven classifier, to map the synthetic design space for colloidal CoO nanoparticles and simultaneously optimize them for multiple catalytically relevant features within a target crystalline phase. The optimized experimental conditions yielded small, phase-pure rock salt CoO nanoparticles of uniform size and shape. These optimized nanoparticles were then supported on SiO 2 and assessed for thermocatalytic CO 2 hydrogenation against larger, polydisperse CoO nanoparticles on SiO 2 and a conventionally prepared catalyst. The optimized CoO/SiO 2 catalyst consistently exhibited higher activity and CH 4 selectivity (ca. 98%) across various pretreatment reduction temperatures as compared to the other catalysts. This remarkable performance was attributed to particle stability and consistent H* surface coverage, even after undergoing the highest temperature reduction, achieving a more stable catalytic species that resists sintering and carbon occlusion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fundamental studies of thermal and electrical transport in microporous metal-organic frameworks

In this work, we established porous metal-organic frameworks (MOFs) as designer conductors of electrons and ions relevant to fundamental research and technological applications. MOFs are porous, crystalline materials composed of organic linkers and inorganic nodes. While most MOFs are insulating with respect to ionic and electronic charge carriers, a number of exceptions have been reported in recent years. Electrically conductive MOFs are highly attractive for applications including electrical energy storage, chemiresistive sensing, and optoelectronics because of their high surface areas and tunable chemical properties. Ion-conducting MOFs are desirable for the synthetically tunable size, shape, and polarity of their pore environments, allowing for the tailored development of solid state electrolytes for metal-ion batteries. We developed systematic strategies for the design of MOFs that conduct ions and electrons. For each objective, we leveraged the versatile chemistry of these materials to obtain frameworks with targeted properties towards electronic or ionic charge carriers. We studied the factors that govern electrical transport in MOFs in order to gain fundamental knowledge of this emerging class of materials. We took several approaches to tackle this problem from multiple angles. Namely, we synthesized and characterized new frameworks, investigated post-synthetic modifications to enhance conductivity, and correlated theory and experiment to uncover new mechanistic findings. These results, which put forth new design principles for conductive MOFs, move the field toward one of the DOE Basic Energy Sciences Grand Challenges: to “design and perfect atom- and energy-efficient synthesis of revolutionary new forms of matter with tailored properties.” In addition to investigating the movement of electrons in MOFs, we also studied the movement of other charged species in MOFs, such as protons, lithium, and magnesium. Proton-conducting frameworks could be appealing materials for solid state electrolytes in fuel cells. In addition, they contain crystallographically defined proton-conducting channels, in contrast with state-of-the-art polymer membranes such as Nafion, which are amorphous. Controlling pore size and polarity in MOFs can thus shed light on proton and other ion transport mechanisms, ultimately enabling the design of more advanced electrolyte materials and potentially novel electrical energy storage materials.

36 MATERIALS SCIENCE↗

Integrating microbial communities into algal biotechnology: a pathway to enhanced commercialization

Microalgae are increasingly recognized for their potential in wastewater treatment and the sustainable production of feedstock for fuel, feed, food, and other bioproducts. Like conventional agricultural systems, algal cultivation involves complex microbial communities. However, despite their pivotal role in cultivation outcomes, especially at the commodity-scale, the critical interactions between microalgae and their microbiomes are often overlooked. Here we synthesize current knowledge on the taxonomic diversity, ecological roles, and biotechnological potential of algal microbiomes, with a focus on their interactions with algal hosts through nutrient exchange, growth modulation, pathogen defense, and environmental conditioning. We also examine how environmental factors such as nutrient availability, salinity, and temperature influence these interactions. Advances in microbiome engineering, including synthetic biology and ecological approaches, offer opportunities to enhance beneficial algal-microbiome interactions, thereby improving growth, resilience, and yield. These advancements could lead to more sustainable and economically viable microalgae cultivation, with far-reaching implications for environmental management and biotechnological innovation. By addressing key economic and environmental barriers, microbiome engineering holds transformative potential to revolutionize large-scale algae cultivation and provide sustainable solutions to global challenges.

Microbiology↗

Sustainable Production of Biomass‐Derived Graphite and Graphene Conductive Inks from Biochar

Abstract Graphite is a commonly used raw material across many industries and the demand for high‐quality graphite has been increasing in recent years, especially as a primary component for lithium‐ion batteries. However, graphite production is currently limited by production shortages, uneven geographical distribution, and significant environmental impacts incurred from conventional processing. Here, an efficient method of synthesizing biomass‐derived graphite from biochar is presented as a sustainable alternative to natural and synthetic graphite. The resulting bio‐graphite equals or exceeds quantitative quality metrics of spheroidized natural graphite, achieving a RamanI D /I G ratio of 0.051 and crystallite size parallel to the graphene layers (L a ) of 2.08 µm. This bio‐graphite is directly applied as a raw input to liquid‐phase exfoliation of graphene for the scalable production of conductive inks. The spin‐coated films from the bio‐graphene ink exhibit the highest conductivity among all biomass‐derived graphene or carbon materials, reaching 3.58 ± 0.16 × 10 4 S m −1 . Life cycle assessment demonstrates that this bio‐graphite requires less fossil fuel and produces reduced greenhouse gas emissions compared to incumbent methods for natural, synthesized, and other bio‐derived graphitic materials. This work thus offers a sustainable, locally adaptable solution for producing state‐of‐the‐art graphite that is suitable for bio‐graphene and other high‐value products.

Chemistry↗

The role of size and structure of catalytic active sites in polyolefin hydrogenolysis

The increasing amount of plastic waste poses serious environmental problems that threaten both ecosystems and human well-being. Hydrogenolysis has been widely studied as an effective approach for converting polyolefins into high-value liquids and waxy fuels. Their multifaceted reaction mechanism, including dehydrogenation, C–C bond cleavage, and hydrogenation, highlights the need for sophisticated catalyst design. The suppression of methane production, a persistent challenge in polyolefin hydrogenolysis, requires precise control of the cleavage site and inhibition of successive C–C bond cleavage. This delicate balance is achieved by carefully tuning the size and structure of metals. In this review, we investigate the effects of the size and structure of active sites on their catalytic activity and selectivity for the hydrogenolysis of polyolefins, including polyethylene and polypropylene. In conclusion, a fundamental understanding of hydrogenolysis mechanisms, combined with strategic synthetic methodologies, is crucial for creating efficient catalysts with tailored properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Multimodal single-Cell/ Particle imaging and engineering for energy conversion in bacteria (Final Technical Report)

Hybrid inorganic-microbial systems have emerged as a potentially transformative approach to combine the light-harvesting capability of inorganic semiconductors and the ability of microbes to orchestrate complex chemical transformations. The objective of this collaborative research is to combine quantum materials synthesis, bacterial synthetic biology, and multimodal single-entity imaging to quantitatively study how hybrid QD-bacteria systems convert light to value chemicals at the single-to-sub cell level, with the ultimate goal of gaining insights to guide the engineering of QDs and bacterial genetics for more efficient bioenergy conversion. The final technical report summarizes our achievements toward this objective.

09 BIOMASS FUELS↗