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At least 631 records · Page 35

BioPhotovoltaics: New paradigm towards high-efficiency and high-stability cells

In this project, we demonstrated significant progress in the development of Bio-Photovoltaic (BioPV) technology, with a particular focus on the transition from the initial success with Artemisinin (ART) to the development of the E1 compound. This journey began with the exploration of less conformationally restricted analogs of ART, leading to the discovery of E1. The initial success in the first quarter with ART set a precedent for the project, guiding our approach in molecular selection and design. Our computational studies provided a solid rationale for selecting specific biomolecules, with density functional theory calculations revealing the potential of certain molecules to form beneficial interactions with perovskite. This was a crucial step in narrowing down the candidate molecules from a broader selection. Subsequently, our approach involved simplifying these molecules to refine their properties and enhance their performance in bioPV applications. The ART-MAPbI3 films, for example, showcased not only high carrier mobility and hydrophobicity but also a significant increase in PCE. The evolution from ART to E1 was marked by a thorough understanding of molecular interactions and their impact on the material’s performance. This progression, from the complexity of lead candidates to the modeling and testing of simplified compounds, has culminated in the development of next-generation biomolecules with vastly improved properties. The link between E1 and ART, through this enhanced understanding, has been compelling and instrumental in achieving the milestones set forth in our project. The success in material and device performance underscores the importance of fundamental molecular design parameters, pointing towards future potential in the field of bioPV technology.

14 SOLAR ENERGY↗

A Mobile Hot Cell for Conditioning Disused Sealed Radioactive Sources for Storage or Transportation

An innovative Mobile Hot Cell (MHC) has been developed for conditioning Disused Sealed Radioactive Sources (DSRS) category 1 and 2 for storage or transportation. The MHC is designed to provide both Radiological and Biological containment with a maximum capacity of 1000 Ci Co60 or 5000Ci Cs137 source and can be transported via standard cargo containers. This project has been supported through the National Nuclear Safety Administration (NNSA) Offsite Source Recovery Program (OSRP). The project is intended for the international community rather than domestic although domestic use is a possibility. Many countries have significant stockpiles of these devices that are often stored in less-than-optimal circumstances. This necessitates that these devices be addressed expeditiously, and the sources secured. The MHC utilizes robotics, automation, and other non-traditional methods for disassembling, characterizing, and packaging these sources that have reached end of life or are otherwise not needed. These innovative approaches are necessary to facilitate an expedited timeline to efficiently and safely secure these sources in a non-proliferation effort. Conditioning efforts include disassembling the device such as a teletherapy head used for cancer treatment, or blood/research irradiators such that the radioactive sources may be removed safely. The sources are then characterized. Leak checks are performed, dimensions are verified, and serial numbers are confirmed. Upon completion, the sources are typically placed into a Standard Forms Capsule which is seal welded closed. It is leak tested and placed into a Long-Term Storage Shield (LTSS) which can either be secured for storage directly or loaded into an appropriate cask for transportation. Further innovations include multiple deployment scenarios that include a full deployment of MHC components, deployment of the MHC automation internal components to an existing hot cell, deployment of minimally required MHC components and incorporation of sand for shielding, and integration of the MHC for Silo Storage, or Bore Hole Storage efforts. The MHC has evolved from a very specific use case to a “Swiss Army Knife” type of a tool in that it can be readily adapted to a large variety of situations. Innovative approaches such as the use of robotics, Computer Numeric Control (CNC) machining centers, automated welding equipment, HDMI Cameras, and LED lighting are some of the developed technologies incorporated into the MHC design. Shielding is accomplished with a steel walled Base Box which is surrounded by four nesting doll shield shells which when combined limits the external dose rate to 5mr/hr when a 1000 Ci Co60 source is exposed inside.

99 - GENERAL AND MISCELLANEOUS↗

Influence of ion-pairing reagents on the separation of intact glycoproteins using hydrophilic-interaction liquid chromatography - high-resolution mass spectrometry

Hydrophilic-interaction liquid chromatography (HILIC) of intact proteins offers high-resolution separations of glycoforms of glycoproteins differing in the number of (neutral) glycans. However, to obtain efficient separations it is essential that the positively charged sites of the proteins are shielded by acidic (negative) ion-pair reagents (IPRs), so as to enhance the contribution of the hydroxyl groups of the (neutral) sugars in the glycoprotein. Here, we studied the influence of various IPRs that differ in physico-chemical properties, such as hydrophobicity and acidity, on the capillary-scale HILIC separation of intact (glyco)proteins. We evaluated the use of fluoroacetic acid (MFA), difluoroacetic acid (DFA), trifluoroacetic acid (TFA), and heptafluorobutyric acid (HFBA) as diluents for sample preparation, as solvents for sample loading on a reversed-phase trap prior to the HILIC separation, and as mobile-phase components for HILIC and HILIC-MS. To reduce the contribution of ion-exchange interaction with the (silica-based) stationary phase, we used an acrylamide-based monolithic column. We studied the influence of the different IPRs on each step of the separation of a mixture of proteins of different size and hydrophilicity and on the separation of the five glycoforms of ribonuclease B. The content of IPR in the sample was shown not to affect the separation and the MS detection. However, a low content of TFA and DFA in the mobile phase is favourable, as it reduces adduct formation and leads to higher signal intensity. The optimized HILIC conditions successfully resolved nine major glycoforms groups of a ~40 kDa glycoprotein horseradish peroxidase (HRP), as an example of a complex glycoprotein.

59 BASIC BIOLOGICAL SCIENCES↗

Polarity effects on wake–up behavior of Al 0.94 B 0.06 N ferroelectrics

Wurtzite ferroelectric materials are promising candidates for energy-efficient memory technologies, particularly for applications requiring high operating temperatures. Asymmetric wake-up behaviors, in which the polarization reversal depends both on polarity and cycle number for the first few dozen cycles, must be better understood for reliable device operation. Here, the detailed analysis of the asymmetric wake-up behavior of thin film Al 0.94 B 0.06 N was performed combining time-resolved switching measurements with Rayleigh analysis, piezoelectric measurements, and etching experiments of progressively switched samples. Furthermore, the analysis shows that the gradual opening of the polarization hysteresis loops associated with wake-up is driven by a gradual increase in the domain-wall density and/or domain-wall mobility with electric field cycle to the polarity opposite to the growth polarity. The insights of this discovery will help to guide interface and polarity design in the eventual deployment of reliable devices based on these materials.

36 MATERIALS SCIENCE↗

Gene network centrality analysis identifies key regulators coordinating day-night metabolic transitions in Synechococcus elongatus PCC 7942 despite limited accuracy in predicting direct regulator-gene interactions

Synechococcus elongatus PCC 7942 is a model organism for studying circadian regulation and bioproduction, where precise temporal control of metabolism significantly impacts photosynthetic efficiency and CO 2 -to-bioproduct conversion. Despite extensive research on core clock components, our understanding of the broader regulatory network orchestrating genome-wide metabolic transitions remains incomplete. We address this gap by applying machine learning tools and network analysis to investigate the transcriptional architecture governing circadian-controlled gene expression. While our approach showed moderate accuracy in predicting individual transcription factor-gene interactions - a common challenge with real expression data - network-level topological analysis successfully revealed the organizational principles of circadian regulation. Our analysis identified distinct regulatory modules coordinating day-night metabolic transitions, with photosynthesis and carbon/nitrogen metabolism controlled by day-phase regulators, while nighttime modules orchestrate glycogen mobilization and redox metabolism. Through network centrality analysis, we identified potentially significant but previously understudied transcriptional regulators: HimA as a putative DNA architecture regulator, and TetR and SrrB as potential coordinators of nighttime metabolism, working alongside established global regulators RpaA and RpaB. This work demonstrates how network-level analysis can extract biologically meaningful insights despite limitations in predicting direct regulatory interactions. The regulatory principles uncovered here advance our understanding of how cyanobacteria coordinate complex metabolic transitions and may inform metabolic engineering strategies for enhanced photosynthetic bioproduction from CO 2 .

59 BASIC BIOLOGICAL SCIENCES↗

Mitigation of the internal p-n junction in CoS 2 -contacted FeS 2 single crystals: Accessing bulk semiconducting transport

Pyrite FeS 2 is an outstanding candidate for a low-cost, nontoxic, sustainable photovoltaic material, but efficient pyrite-based solar cells are yet to materialize. Recent studies of single crystals have shed much light on this by uncovering a p-type surface inversion layer on n-type (S-vacancy doped) crystals, and the resulting internal p-n junction. This leaky internal junction likely plays a key role in limiting efficiency in pyrite-based photovoltaic devices, also obscuring the true bulk semiconducting transport properties of pyrite crystals. Here, we demonstrate complete mitigation of the internal p-n junction in FeS 2 crystals by fabricating metallic CoS 2 contacts via a process that simultaneously diffuses Co (a shallow donor) into the crystal, the resulting heavy n doping yielding direct Ohmic contact to the interior. Low-temperature bulk transport studies of controllably Co- and S-vacancy doped semiconducting crystals then enable a host of previously inaccessible observations and measurements, including determination of donor activation energies (which are as low as 5 meV for Co), observation of an unexpected second activated transport regime, realization of electron mobility up to 2100 cm 2 V –1 s –1 , elucidation of very different mobilities in Co- and S-vacancy-doped cases, and observation of an abrupt temperaturedependent crossover to bulk Efros-Shklovskii variable-range hopping, accompanied by an unusual form of nonlinear Hall effect. Aspects of the results are interpreted with the aid of first-principles electronic structure calculations on both Co- and S-vacancy-doped FeS 2 . Furthermore, this work thus demonstrates unequivocal mitigation of the internal p-n junction in pyrite single crystals, with important implications for both future fundamental studies and photovoltaic devices

36 MATERIALS SCIENCE↗

Thermochemically-Informed Mass Transport Model for Zr in U-Zr Fuel

Recent improvements to the coupled Thermochimica-MOOSE/BISON code system have enabled efficient calculations of species transport based on direct evaluation of composition and temperature dependent chemical potentials of the species. This presents an alternative to the traditional approach to species transport in nuclear fuels, which has been to employ a diffusion formulation that combines concentration-gradient driven Fickian diffusion with a Soret term based on a heat of transport fit to experimental data. Here we describe the application of the coupled code system to the diffusion of Zr in U-Zr metallic fuel. New classes implemented in BISON to solve this problem are documented. The Zr concentration profile after 50 years of diffusion is found to be strongly dependent on the assumptions made pertaining how to mobility is calculated in multi-phase regions of the fuel element. Two assumptions are compared (simple averaging of mobilities and using the majority phase mobility), and good qualitative agreement with experimental measurements is obtained using the majority phase assumption.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

MZA: A Data Conversion Tool to Facilitate Software Development and Artificial Intelligence Research in Multidimensional Mass Spectrometry

Modern mass spectrometry-based workflows employing hybrid instrumentation and orthogonal separations collect multidimensional data, potentially allowing deeper understanding in omics studies through adoption of artificial intelligence methods. However, the large volume of these rich data challenges existing data storage and access technologies, therefore precluding informatics advancements. Here we present MZA™ (pronounced m-za), the mass-to-charge (m/z) generic data storage and access tool designed to facilitate software development and artificial intelligence research in multidimensional mass spectrometry measurements. Composed by a data conversion tool and a simple file structure based on the HDF5 format, MZA provides easy, cross-platform and efficient programmatic access to raw MS-data, enabling fast development of new tools in data science programming languages such as Python and R. The software executable and example Python and R scripts are freely available at https://github.com/PNNL-m-q/mza.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Search for active and inactive ion insertion sites in organic crystalline materials

The position of mobile active and inactive ions, specifically ion insertion sites, within organic crystals, significantly affects the properties of organic materials used for energy storage and ionic transport. Identifying the positions of these atomic (and ionic) sites in an organic crystal is challenging, especially when the element has low X-ray scattering power, such as lithium (Li) and hydrogen, which are difficult to detect by powder X-ray diffraction. First-principles calculations, exemplified by density functional theory (DFT), are very practical for confirming the relative stability of ion positions in materials. However, the lack of effective strategies to identify ion sites in these organic crystalline frameworks renders this task extremely challenging. This work presents two algorithms: the (i) efficient location of ion insertion sites from extrema in electrostatic local potential and charge density (ELIISE), and the (ii) ElectRostatic InsertioN (ERIN), which leverage charge density and electrostatic potential fields accessed from first-principles calculations, combined with the Simultaneous Ion Insertion and Evaluation (SIIE) workflow. SIIE inserts all ions simultaneously—to determine ion positions in organic crystals. We demonstrate that these methods accurately reproduce known ion positions in 16 organic materials and identify previously overlooked low-energy sites in tetralithium 2,6-naphthalenedicarboxylate (Li4NDC), an organic electrode material, highlighting the importance of inserting all ions simultaneously, as in the SIIE workflow. These algorithms are also integrated with off-the-shelf machine learning potentials, yielding promising results comparable to first-principles findings.

Gopidi, Harshan Reddy [Argonne National Laboratory↗

Transportation Energy Data Book: Edition 38

The Transportation Energy Data Book: Edition 38 is a statistical compendium prepared and published by Oak Ridge National Laboratory (ORNL) under contract with the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, Vehicle Technologies Office. Designed for use as a desk-top reference, the Data Book represents an assembly and display of statistics and information that characterize transportation activity, and presents data on other factors that influence transportation energy use. The purpose of this document is to present relevant statistical data in the form of tables and graphs. The latest edition of the Data Book is available via the Internet. This edition of the Data Book has 13 chapters which focus on various aspects of the transportation industry. Chapter 1 - focuses on petroleum; Chapter 2 - energy; Chapter 3 - highway vehicles; Chapter 4 - light vehicles; Chapter 5 - heavy vehicles; Chapter 6 - alternative fuel vehicles; Chapter 7 - transit and shared mobility; Chapter 8 - fleet vehicles; Chapter 9 - household vehicles; Chapter 10 - nonhighway modes; Chapter 11 - transportation and the economy; Chapter 12 - greenhouse gas emissions; and Chapter 13 - criteria pollutant emissions. The sources used represent the latest available data. There are also three appendices which include detailed source information for some tables, measures of conversion, and energy tables and figures with electricity generation and distribution taken into account. A glossary of terms is also included for the reader’s convenience.

02 PETROLEUM↗

Precision Synthesis of Conjugated Polymer Films by Surface-Confined Stepwise Sonogashira Cross-Coupling

Thin films of poly(arylene ethynylene)-conjugated polymers, including low-energy-gap donor–acceptor polymers, can be prepared via stepwise polymerization utilizing surface-confined Sonogashira cross-coupling. This robust and efficient polymerization protocol yields conjugated polymers with a precise molecular structure and with nanometer-level control of the organization and the uniform alignment of the macromolecular chains in the densely packed film. In addition to high stability and predictable and well-defined molecular organization and morphology, the surface-confined conjugated polymer chains experience significant interchain electronic interactions, resulting in dominating intermolecular π-electron delocalization which is primarily responsible for the electronic and spectroscopic properties of polymer films. The fluorescent films demonstrate remarkable performance in chemosensing applications, showing a turn-off fluorescent response on the sub-ppt (part per trillion) level of nitroaromatic explosives in water. This unique sensitivity is likely related to the enhanced exciton mobility in the uniformly aligned and structurally monodisperse polymer films.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Single-Particle Measurements Reveal the Origin of Low Solar-to-Hydrogen Efficiency of Rh-Doped SrTiO 3 Photocatalysts

Solar-powered photochemical water splitting using suspensions of photocatalyst nanoparticles is an attractive route for economical production of green hydrogen. SrTiO 3 -based photocatalysts have been intensely investigated due to their stability and recently demonstrated near-100% external quantum yield (EQY) for water splitting using wavelengths below 360 nm. To extend the optical absorption into the visible, SrTiO 3 nanoparticles have been doped with various transition metals. Here, in this work, we demonstrate that doping SrTiO 3 nanoparticles with 1% Rh introduces midgap acceptor states which reduce the free electron concentration by 5 orders of magnitude, dramatically reducing built-in potentials which could otherwise separate electron–hole (e–h) pairs. Rhodium states also function as recombination centers, reducing the photocarrier lifetime by nearly 2 orders of magnitude and the maximum achievable EQY to 10%. Furthermore, the absence of built-in electric fields within Rh-doped SrTiO 3 nanoparticles suggests that modest e–h separation can be achieved by exploiting a difference in mobility between electrons and holes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Approaches to investigate the role of chelation in the corrosivity of biomass-derived oils

The need to provide the U.S. market with a renewable liquid fuel energy source from a non-food feedstock stream has gained considerable traction due to benefits such as improved energy efficiency, reduced environmental impacts, and enhanced national security. Practical achievement of these goals via biomass and bio-waste utilization involves production of liquid intermediates containing corrosive, reactive species like carboxylic acids, ketones, aldehydes, and hydroxyaldehydes. Such mixtures challenge materials of containment, processing, and transport. It is widely recognized that the smaller organic acids, such as acetic and formic, are corrosive and can remove protective surface oxides on alloys used in bio-oil processing infrastructure, and ketones can swell sealing polymers. However, literature shows, and findings herein confirm, larger carboxylic acids and bidentate alcohols are present. This highlights the potential for synergistic, detrimental effects of constituents in bio-oil corrosion, including direct reactivity of small acids compounded with the possibility of mobilization of protective metal oxide layers via chelation by larger acids and oxygenates. The question of whether species beyond small acids can significantly contribute to corrosion requires analytical approaches previously not applied to bio-oil corrosion studies and certainly not previously applied corroboratively. As such, this work introduces a combination of optical, mass spectral, and electrochemical impedance spectroscopies with an incubation approach to study metal mobilization, to facilitate elucidating chelation's role in bio-oil corrosive pathways. To enable systematic study of these oxygenates' material compatibility individually and in combination, a model matrix of bio-oil constituents was also developed based on identification of key components of real bio-oils.

09 BIOMASS FUELS↗

New sterically hindered polyvinylamine-containing membranes for CO 2 capture from flue gas

Amine-containing facilitated transport membranes can have both high permeability and selectivity due to the reversible reaction between CO 2 and amino groups for effective carbon capture from flue gas. In this study, we have developed an improved method for the synthesis of high-molecular-weight sterically hindered polyvinylamine (PVAm) as the new fixed-site carrier in thin-film composite membranes for CO 2 capture. Commercially available PVAm was N-monomethylated into poly-N-methyl-N-vinylamine (PVAm-CH 3 ) using the stepwise reductive amination with a highly polar fluorinated alcohol as the solvent to enhance the equilibrium shift to the formation of the imine intermediate. The method prevented over-alkylation, resulting in the increased yield of the target product. PVAm-CH 3 exhibited excellent CO 2 facilitation with a CO 2 permeability of 445.7 Barrer (1 Barrer = 3.349 x 10 –16 mol m m –2 s –1 Pa –1 ) and a CO 2 /N 2 selectivity of 70.3, which are above the Robeson 2008 upper bound. The PVAm-CH 3 solution retained a sufficiently high viscosity after incorporating the aminoacid salt, 2-(1-piperazinyl)ethylamine sarcosinate (PZEA-Sar), as the mobile carrier for the membrane coating on nanoporous polyethersulfone (PES) substrates without any penetration issues. The resultant thin-film composite PVAm-CH3/PZEA-Sar membrane with a thickness of approximately 170 nm exhibited a superior CO 2 performance of 1071 GPU (1 GPU = 3.349 x 10 –10 mol m –2 s –1 Pa –1 ) and a CO 2 /N 2 selectivity of 183 at 57°C and a feed gas pressure of 111.64 kPa (1.5 psig). This PVAm-CH 3 /PZEA-Sar membrane surpassed the latest redefined 2019 CO 2 /N 2 upper bound and outperformed other polymer-based membranes. Density functional theory calculations also demonstrated that PVAm-CH 3 showed a stronger preference, relative to PVAm, toward the more efficient bicarbonate pathway. Thus, the steric hindrance effect of PVAm-CH 3 enhanced the solubility of CO 2 in the polymer matrix and resulted in the higher CO 2 permeance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Quantifying Phospholipids in Organic Samples Using a Hydrophilic Interaction Liquid Chromatography–Inductively Coupled Plasma High-Resolution Mass Spectrometry (HILIC-ICP-HRMS) Method

Here, in this study, a novel method using hydrophilic interaction liquid chromatography (HILIC) coupled with inductively coupled plasma high-resolution mass spectrometry (ICP-HRMS) was introduced for the quantification of phospholipids in oil samples. The method employed a bridged ethyl hybrid (BEH) stationary phase HILIC column with a tetrahydrofuran (THF)/water mobile phase, enhancing the solubility and detection of phospholipids. During the study, a gradient/matrix effect on ICP-HRMS sensitivity was observed and successfully compensated for experimentally, ensuring reliable quantification results. This approach has proven effective for a wide range of different oil samples including vegetable oils, animal fats, and phospholipid supplements. Notably, this method allowed the direct quantification of phospholipids in oil samples, bypassing the need for prior sample preparation methods, such as solid phase extraction (SPE), thereby streamlining the analytical process. The precision, accuracy, and reduced need for extensive sample preparation offered by this method mark a significant advancement in lipids analysis. Its robustness and broad applicability have substantial implications for industries such as food and renewable energy production, where both efficient and accurate lipid identification and quantification are crucial.

09 BIOMASS FUELS↗

Transportation Energy Data Book: Edition 39

The Transportation Energy Data Book: Edition 39 is a statistical compendium prepared and published by Oak Ridge National Laboratory (ORNL) under contract with the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, Vehicle Technologies Office. Designed for use as a desk-top reference, the Data Book represents an assembly and display of statistics and information that characterize transportation activity and presents data on other factors that influence transportation energy use. The purpose of this document is to present relevant statistical data in the form of tables and graphs. The latest edition of the Data Book is available via the Internet (tedb.ornl.gov).This edition of the Data Book has 13 chapters which focus on various aspects of the transportation industry. Chapter 1 focuses on petroleum; Chapter 2 – energy; Chapter 3 – highway vehicles; Chapter 4 – light vehicles; Chapter 5 – heavy vehicles; Chapter 6 – alternative fuel vehicles; Chapter 7 – transit and other shared mobility; Chapter 8 – fleet vehicles; Chapter 9 – household vehicles; Chapter 10 – nonhighway modes; Chapter 11 – transportation and the economy; Chapter 12 – greenhouse gas emissions; and Chapter 13 – criteria pollutant emissions. The sources used represent the latest available data. There are also three appendices which include detailed source information for some tables, measures of conversion, and energy tables with electricity generation and distribution. A glossary of terms is also included for the reader’s convenience.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Transportation Energy Data Book (Edition 40)

The Transportation Energy Data Book: Edition 40 is a statistical compendium prepared and published by Oak Ridge National Laboratory (ORNL) under contract with the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, Vehicle Technologies Office. Designed for use as a desk-top reference, the Data Book represents an assembly and display of statistics and information that characterize transportation activity and presents data on other factors that influence transportation energy use. The purpose of this document is to present relevant statistical data in the form of tables and graphs. The latest edition of the Data Book is available via the Internet (tedb.ornl.gov).This edition of the Data Book has 13 chapters which focus on various aspects of the transportation industry. Chapter 1 focuses on petroleum; Chapter 2 – energy; Chapter 3 – highway vehicles; Chapter 4 – light vehicles; Chapter 5 – heavy vehicles; Chapter 6 – alternative fuel vehicles; Chapter 7 – transit and other shared mobility; Chapter 8 – fleet vehicles; Chapter 9 – household vehicles; Chapter 10 – nonhighway modes; Chapter 11 – transportation and the economy; Chapter 12 – greenhouse gas emissions; and Chapter 13 – criteria pollutant emissions. The sources used represent the latest available data. There are also two appendices which include detailed source information for some tables and measures of conversion. A glossary of terms is also included for the reader’s convenience.

02 PETROLEUM↗