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Supramolecular assembly of polycation/mRNA nanoparticles and in vivo monocyte programming

Size-dependent phagocytosis is a well-characterized phenomenon in monocytes and macrophages. However, this size effect for preferential gene delivery to these important cell targets has not been fully exploited because commonly adopted stabilization methods for electrostatically complexed nucleic acid nanoparticles, such as PEGylation and charge repulsion, typically arrest the vehicle size below 200 nm. Here, we bridge the technical gap in scalable synthesis of larger submicron gene delivery vehicles by electrostatic self-assembly of charged nanoparticles, facilitated by a polymer structurally designed to modulate internanoparticle Coulombic and van der Waals forces. Specifically, our strategy permits controlled assembly of small poly(β-amino ester)/messenger ribonucleic acid (mRNA) nanoparticles into particles with a size that is kinetically tunable between 200 and 1,000 nm with high colloidal stability in physiological media. We found that assembled particles with an average size of 400 nm safely and most efficiently transfect monocytes following intravenous administration and mediate their differentiation into macrophages in the periphery. When a CpG adjuvant is co-loaded into the particles with an antigen mRNA, the monocytes differentiate into inflammatory dendritic cells and prime adaptive anticancer immunity in the tumor-draining lymph node. This platform technology offers a unique ligand-independent, particle-size-mediated strategy for preferential mRNA delivery and enables therapeutic paradigmsviamonocyte programming.

Science & Technology - Other Topics↗

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

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

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Using interfaces to: create strongly-coupled magnetic-ferroelectrics

Starting at the level of electrons and atoms our long-term goal is to rationally design complex oxide heterostructures and interface-materials with targeted emergent behaviors. This is not a matter of simply optimizing material parameters, but rather begins with understanding a mechanism to control the interplay between the diverse microscopic degrees of freedom prevalent in complex oxides in order to create targeted macroscopic phenomena and ends with the design of new material realizations. These realizations are in turn created with atomic-layer precision, structurally assessed to see that they are the intended realization, and finally their relevant properties are measured. During this program we have developed the scientific ideas necessary to apply this materials-by-design paradigm to the creation of materials offering electrical control of magnetism. At the heart of our approach lies a partnership between theory, synthesis, and characterization. These are the areas of expertise of the three co-PIs, who have worked closely together since their arrival at Cornell. During this project bold ideas on where to put the atoms to provide electrical control of magnetism were met with the latest methods of synthesis science and electron microscopy in an attempt create targeted new multiferroics. Our work applying this materials-by-design methodology to multiferroics has enjoyed multiple successes. The Co-PIs have invented new mechanisms for multiferroics, which provide strong coupling between polarization and magnetism, and reduced them to practice. Specifically, we pioneered multiferroics based on spin-phonon coupling, rotation-driven multiferroicity, and novel geometric multiferroics. Importantly, the latter two of these mechanisms enable the deterministic switching of magnetism by an applied electric field, which is key to the application of multiferroics to future device technologies. Most recently, we performed detailed theoretical analysis on a system involving the combination of magnetoelectric and colossal magnetoresistance behaviors and predict that electrical control of a metal-insulator transition is possible in appropriately strained SmBaMn2O6. The research enabled by this grant led to 63 publications in leading refereed journals including Nature, Nature Materials, Physical Review Letters, and Advanced Materials demonstrating a materials-by-design paradigm to the creation of materials offering electrical control of magnetism.

36 MATERIALS SCIENCE↗

Paths to superheavy nuclei

This document summarizes the discussions and outcomes of the Facility for Rare Isotope Beams (FRIB) Theory Alliance topical program ‘The path to Superheavy Isotopes’ held in June 2024 at FRIB. Its content is non-exhaustive, reflecting topics chosen and discussed by the participants. The program aimed to assess the current status of theory in superheavy nuclei (SHN) research and identify necessary theoretical developments to guide experimental programs and determine fruitful production mechanisms. This report details the intersection of SHN research with other fields, provides an overview of production mechanisms and theoretical models, discusses future needs in theory and experiment, explores other potential avenues for SHN synthesis, and highlights the importance of building a strong theory community in this area.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Early Career: Mesoscale Fragments of Crystalline Silicon by Chemical Synthesis (Final Technical Report)

Silicon has transformed the modern era, with applications in computing, solar cells, energy storage, and beyond. The traditional approach to making silicon is a high-temperature “top-down” process that affords only the most stable form of silicon, leaving hidden vast swathes of structure-function space. The goal of this program was to establish new approaches to making silicon-based materials from the bottom-up, allowing structural precision from the atomic level up to the bulk, and to understand how structure influences function. Key results included the development of the cyclosilane building blocks and low-temperature methods for their polymerization, as well as new tools for spectroscopic characterization. In addition to revealing new materials chemistry insights, in the five-year period covered by this award, this work resulted in 11 publications and three graduate student theses.

36 MATERIALS SCIENCE↗

Convergence QL: NSF/DOE Quantum Science Summer School: QS3 Final Report

Convergence QL: NSF/DOE Quantum Science Summer School (QS3) was a 2-week summer program held in 2017, 2018, 2019, and 2022. The program was aimed at graduate students and postdoctoral researchers working on a wide range of topics related to quantum science and quantum engineering. Expert leaders in this field served as lectures for the school. The school program included lectures, active learning, project activities, poster presentations, and industry panel discussions. The school covered four topics: Fundamentals and Applications of Quantum Computing (2017), Fundamentals and Applications of Quantum Materials (2018), Fundamentals and Applications of Quantum Devices (2019), and Modern Synthesis of Quantum Materials (2022). In terms of intellectual merit, the school brought together students from different areas of research related to quantum science to educate them on a broad range of related topics, providing a unique crucible for the development of educational content and learning opportunities in a cross-disciplinary fashion in the context of quantum science and quantum engineering. In terms of broader impacts, this may serve to create a workforce which would accelerate research in quantum science, quantum engineering, and the development of new quantum technologies beneficial to society. Additionally, this may add to the training of a cadre of scientists and engineers to serve as future leaders in this research field.

42 ENGINEERING↗

Ion Mobility Spectrometry Characterization of the Intermediate Hydrogen-Containing Gold Cluster Au7(PPh3)7H52+

We employ ion mobility spectrometry and density functional theory to determine the structure of Au7(PPh3)7H52+ (PPh3 = triphenylphosphine) which was recently identified by high mass resolution mass spectrometry. Experimental ion-neutral collision cross sections represent the momentum transfer between the ionic clusters and gas molecules averaged over the relative thermal velocities of the colliding pair, thereby providing structural insights. Theoretical calculations indicate the geometry of Au7(PPh3)7H52+ is similar to Au7(PPh3)7+, with three hydrogen atoms bridging two gold atoms and two hydrogen atoms forming single Au–H bonds. Collision induced dissociation products observed during IMS experiments reveal that smaller hydrogen containing clusters may be produced through fragmentation of Au7(PPh3)7H52+. Our findings indicate that hydrogen containing species like Au7(PPh3)7H52+ act as intermediates in the formation of larger phosphine ligated gold clusters. These results advance the understanding and ability to control the mechanisms of size selective cluster formation which is necessary for scalable synthesis of clusters with tailored properties. This work was supported by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. M.A.H. acknowledges support from the DOE Science Undergraduate Laboratory Internship (SULI) program. H.H. acknowledges support from the DOE Office of Workforce Development for Teachers and Scientist (WDTS) under the Visiting Faculty Program (VFP). The efforts of K.A.M. and B.H.C. were supported by the Defense Threat Reduction Agency (Grant No. HDTRA1-14-1-0023). The research was performed using EMSL, a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated by Battelle for DOE under Contract DE-AC05-76RL01830.

Ligare, Marshall R.↗

Fischer-Tropsch Synthesis: The Characterization and Testing of Pt-Co/SiO 2 Catalysts Prepared with Alternative Cobalt Precursors

Different low-cost cobalt precursors (acetate, chloride) and thermal treatments (air calcination/H 2 reduction versus direct H 2 -activation) were investigated to alter the interaction between cobalt and silica. H 2 -activated catalysts prepared from cobalt chloride had large Co 0 particles (XRD, chemisorption) formed by weak interactions between cobalt chloride and silica (temperature programmed reduction (TPR), TPR with mass spectrometry (TPR-MS), TPR with extended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge spectroscopy (XANES) techniques) and retained Cl-blocked active sites, resulting in poor activity. In contrast, unpromoted Co/SiO 2 catalysts derived from cobalt acetate had strong interactions between Co species and silica (TPR/TPR-MS, TPR-EXAFS/XANES); adding Pt increased the extent of the Co reduction. For these Pt-promoted catalysts, the reduction of uncalcined catalysts was faster, resulting in larger Co 0 clusters (19.5 nm) in comparison with the air-calcined/H 2 -activated catalyst (7.8 nm). Both catalysts had CO conversions 25% higher than that of the Pt-promoted catalyst prepared in the traditional manner (air calcination/H 2 reduction using cobalt nitrate) and three times higher than that of the traditional unpromoted Co/silica catalyst. The retention of residual cobalt carbide (observed in XANES) from cobalt acetate decomposition impacted performance, resulting in a higher C 1 –C 4 selectivity (32.2% for air-calcined and 38.7% for uncalcined) than that of traditional catalysts (17.5–18.6%). The residual carbide also lowered the α-value and olefin/paraffin ratio. Future work will focus on improving selectivity through oxidation–reduction cycles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enhanced stability of Fe-modified CuO-ZnO-ZrO 2 -Al 2 O 3 /HZSM-5 bifunctional catalysts for dimethyl ether synthesis from CO 2 hydrogenation

In this report a series of iron (Fe) modified CuO-ZnO-ZrO 2 -Al 2 O 3 (CZZA) catalysts, with various Fe loadings, were prepared using a co-precipitation method. A bifunctional catalyst, consisting of Fe-modified CZZA and HZSM-5, was studied for dimethyl ether (DME) synthesis via CO 2 hydrogenation. The effects of Fe loading, reaction temperature, reaction pressure, space velocity, and concentrations of precursor for the synthesis of the Fe-modified CZZA catalyst on the catalytic activity of DME synthesis were investigated. Long-term stability tests showed that Fe modification of the CZZA catalyst improved the catalyst stability for DME synthesis via CO 2 hydrogenation. The activity loss, in terms of DME yield, was significantly reduced from 4.2% to 1.4% in a 100 h run of reaction, when the Fe loading amount was 0.5 (molar ratio of Fe to Cu). An analysis of hydrogen temperature programmed reduction revealed that the introduction of Fe improved the reducibility of the catalysts, due to assisted adsorption of H 2 on iron oxide. The good stability of Fe-modified CZZA catalysts in the DME formation was most likely attributed to oxygen spillover that was introduced by the addition of iron oxide. This could have inhibited the oxidation of the Cu surface and enhanced the thermal stability of copper during long-term reactions.

42 ENGINEERING↗

Advanced Research Directions on AI for Science, Energy, and Security: Report on Summer 2022 Workshops

Over the past decade, fundamental changes in artificial intelligence (AI)—from foundational to applied—have delivered dramatic insights across a wide breadth of U.S. Department of Energy (DOE) mission space. AI is helping to augment and improve scientific and engineering workflows (e.g., for control, design, and dramatic performance gains through surrogate models) in national security, the Office of Science, and DOE’s applied energy programs. The progress and potential for AI in DOE science was captured in the 2020 “AI for Science” report from the DOE laboratory community in collaboration with academia and industry. Specific scientific areas ready to further leverage the power of AI ranged from the scale and performance of computational models to data analysis to creating new classes of observations using computer vision. Since that report, the scale and scope of scientific AI have accelerated, revealing new, emergent properties that yield insights that go beyond enabling opportunities to being potentially transformative in the way that scientific problems are posed and solved. Thus, under the guidance of both the Office of Science (SC) and the National Nuclear Security Administration (NNSA), the DOE national laboratories organized a series of workshops in 2022 to gather input on new and rapidly emerging opportunities and challenges of scientific AI. This 2023 report is a synthesis of those workshops. The scientific community believes AI can have a foundational impact on a broad range of DOE missions, including science, energy, and national security. Further, DOE has unique capabilities that enable the community to drive progress in scientific use of AI, building on long-standing DOE strengths and investments in computation, data, and communications infrastructure, spanning the Energy Sciences Network (ESnet), the Exascale Computing Project (ECP), and integrative programs such as the NNSA Office of Defense Programs Advanced Simulation and Computing (ASC) and the SC Scientific Discovery through Advanced Computing (SciDAC) programs.

97 MATHEMATICS AND COMPUTING↗

Divanadium substituted keggin [PV 2 W 10 O 40 ] on non-reducible supports-Al 2 O 3 and SiO 2 : synthesis, characterization, and catalytic properties for oxidative dehydrogenation of propane

Molecular metal oxide cluster, K 5 [α-1,2-PV 2 W 10 O 40 ] (PV 2 W 10 ), was found to have intrinsic catalytic activity for the oxidative dehydrogenation of propane with high selectivity (> 80%) to propylene at low propane conversion (0.3%). Synthesis of dispersed PV 2 W 10 in non-reducible supports, γ-Al 2 O 3 and SiO 2 , was done by incipient wetness impregnation. The supported catalysts were characterized by IR, Raman spectroscopy, nitrogen adsorption, x-ray powder diffraction (PXRD), elemental analysis, hydrogen temperature-programmed reduction (H 2 –TPR), and ammonia temperature-programmed desorption (NH 3 –TPD). Catalytic testing of the supported PV 2 W 10 at equimolar cluster concentration revealed that when supported in γ-Al 2 O 3 it is more active (sevenfold increase in propane conversion) but in SiO 2 it is more selective to propylene (94%). The observed performance was due to both an increase in reducibility and higher concentration of strong acid sites for PV 2 W 10 supported in γ-Al 2 O 3 versus SiO 2 . Lastly, PV 2 W10 was shown to remain intact under reaction conditions indicating its thermal and oxidative stability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Methanol from Integrated Direct Air Capture and Ceramic Electrolysis (MIDACE)

The Methanol from Integrated Direct Air Capture and Ceramic Electrolysis (MIDACE) project advanced a novel system concept for integrating pressurized co-electrolysis of steam and crude carbon dioxide captured directly from ambient air using a sorbent technology. The co-electrolysis produced syngas provides feedstock for a gas-to-liquid methanol synthesis reactor. The system recovers waste heat from the reactor and electrolyzer into regenerating the direct air capture sorbent. The purpose of the project was to demonstrate critical integration elements of the design and perform a technical study illustrating how a large-scale installation could achieve the $800/ton program target for green methanol production. The concept addresses the program objective to consolidate operations by combining crude CO 2 cleanup, hydrogen production, and partial CO 2 reduction steps within a carbon tolerant high temperature electrolyzer. The design lowers costs by simplifying the methanol recovery cycle, reducing carbon losses from venting, reducing sensitivity to catalyst selectivity, and avoiding syngas compression.

10 SYNTHETIC FUELS↗

Selective Conversion of CO 2 to Methanol on a In 2 O 3– x –TiO 2 (110) Interface: Importance of Oxide–Oxide Interactions

Methanol is a strategic energy vector for the storage and delivery of energy and is a widely used precursor for the synthesis of many high-value chemicals. The hydrogenation of carbon dioxide (CO 2 ) into methanol is a key process in industrial operations. Here, in this study, we show that an oxide-oxide interface generated by a low loading (0.15 ML) of In 2 O 3-x on a TiO 2 (110) substrate has a high activity and selectivity as a catalyst for the CO 2 + 3H 2 → CH 3 OH + H 2 O process. The properties of the In 2 O 3-x -TiO 2 interface under reaction conditions were investigated using a combination of synchrotron-based ambient pressure X-ray photoelectron spectroscopy (AP-XPS), temperature programmed desorption (TPD), and catalytic testing. The In 2 O 3-x overlayer spread out on top of the titania and was rich in defects and O vacancies that activated CO 2 and H 2 as reactants, without destroying CH 3 O and CH 3 OH as reaction products. The In 2 O 3-x /TiO 2 (110) catalyst is at least one order of magnitude more active than bulk indium oxide while maintaining a very high selectivity (~80%) towards methanol production. Under the rich hydrogen environment of methanol synthesis, the oxide-oxide interactions allowed only a partial reduction of the In cations, preventing the formation of metal alloys as seen in the case of catalysts with metal-indium oxide interfaces. Thus, the dispersion of low loadings of In 2 O 3-x on a stable oxide substrate is a valid and low-cost approach for generating efficient catalysts for CO 2 valorization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Toward Evaluating High-Level Synthesis Portability and Performance between Intel and Xilinx FPGAs

Offloading computation from a CPU to a hardware accelerator is becoming a more common solution for improving performance because traditional gains enabled by Moore’s law and Dennard scaling have slowed. GPUs are often used as hardware accelerators, but field-programmable gate arrays (FPGAs) are gaining traction. FPGAs are beneficial because they allow hardware specific to a particular application to be created. However, they are notoriously difficult to program. To this end, two of the main FPGA manufacturers, Intel and Xilinx, have created tools and frameworks that enable the use of higher level languages to design FPGA hardware. Although Xilinx kernels can be designed by using C/C++, both Intel and Xilinx support the use of OpenCL C to architect FPGA hardware. However, not much is known about the portability and performance between these two device families other than the fact that it is theoretically possible to synthesize a kernel meant for Intel to Xilinx and vice versa.In this work, we evaluate the portability and performance of Intel and Xilinx kernels. We use OpenCL C implementations of a subset of the Rodinia benchmarking suite that were designed for an Intel FPGA and make the necessary modifications to create synthesizable OpenCL C kernels for a Xilinx FPGA. We find that the difficulty of porting certain kernel optimizations varies, depending on the construct. Once the minimum amount of modifications is made to create synthesizable hardware for the Xilinx platform, more nontrivial work is needed to improve performance. However, we find that constructs that are known to be performant for an FPGA should improve performance regardless of the platform; the difficulty comes in deciding how to invoke certain kernel optimizations while also abiding by the constraints enforced by a given platform’s hardware compiler.

Cabrera, Anthony↗

High-Performance Low-Cobalt Cathode Materials for Li-ion Batteries

The layer-structured Li[Ni x Co y Mn 1-x-y ]O 2 (NCM) cathode materials have been the best choice for increasing electric vehicle driving distance per charge. The high Ni layered oxide represents successfully commercialized NCM cathodes (such as NCM622 and NCA) in lithium-ion batteries (LIBs) for EV applications due to their high energy density and acceptable cycling stability. However, the price of cobalt, the key element within LIBs for stability, has nearly tripled over the past few years due to increased demand from the cell phone industry. As mentioned in the DOE Funding Opportunity Announcement, the current materials shortage will also cause speculation for a future global shortage. Therefore, to meet the requirement and sustainability of the next-generation long-range and low-cost EVs, developing cathode materials with low-Co content to achieve higher energy density and lower cost is both essential and urgent. The overarching objective of this work is to develop stabilized NCM cathode materials with low Co content (namely LiNi x Co y Mn 1-x-y O 2 , y ≤ 0.04) to meet DOE’s goal of reducing Co loading below 50 mg Wh -1 while maintaining energy density greater than 600 Wh kg -1 based on cathode material. Via various dopings and coatings scalable methods, we explored and enhanced the cycling performance of low-cobalt cathodes. The final obtained NCM cathodes paired with graphite anode aim to deliver batteries with a high initial specific energy density of over 240 Wh kg -1 and a low capacity fading rate of less than 20% in 1000 cycles under a C/3 discharge rate. To accomplish this goal, a multidisciplinary team with several co-investigators has been formed from three organizations: The Pennsylvania State University (PSU), Oak Ridge National Laboratory (ORNL), and Pacific Northwest National Laboratory (PNNL). The PI and co-investigators are Dr. Donghai Wang (PI) from PSU with expertise in the synthesis of nanostructured materials and manipulation of interfacial properties of electrochemically active materials, Dr. Jagjit Nanda, with substantial knowledge of and expertise in state-of-the-art cathodes from ORNL, Dr. Chao-Yang Wang with significant experience in advanced cell design and fabrication and cell diagnostics from PSU, and Dr. Chongmin Wang with world-wide known expertise of advance atomic scale characterization of electrode materials from PNNL. Furthermore, this project will leverage and synergistically work with the current DOE-funded programs on battery materials at PSU and ORNL and electrode materials characterization at PNNL. During this funded period, we have accomplished milestones stated as follows: • Scale up production of LiFePO 4 (LFP) coated NCM811 with a production of 300g/batch. Fifteen (≥2 Ah) pouch cells with LFP-coated NCM811 cathode are delivered. Self-evaluated pouch cells in PSU show superior over 80% capacity retention performance even after 1500 cycles at C/3 rate. • Various cations (Al, Ti, Zr, and Mo) substitute cobalt in low-cobalt partially and Co-free cathodes. Their effects on crystal structure and electrochemical behavior are explored. • Phosphate compounds as coating materials represent promising surface protection precursors for low-cobalt cathode materials. Therefore, several metal phosphates were selected for improving the NMC cycling performance and are regarded as effective approaches for a scalable and practical surface protection method. • Production of NCM92, where Nickel content is 92% among transition metals, is scaled up from synthesis to coating and heat treatment procedures. Fifteen 2.7Ah pouch cells with Ti-doped NCM92 cathodes and industrial graphite anode are delivered to Idaho National Lab for testing.

25 ENERGY STORAGE↗

Comparison of Quinone-Based Catholytes for Aqueous Redox Flow Batteries and Demonstration of Long-Term Stability with Tetrasubstituted Quinones

Quinones are appealing targets as organic electrolytes for aqueous redox flow batteries (RFBs), but their utility continues to be constrained by limited stability under operating conditions. The present study evaluates the stability of a series water-soluble quinones, with redox potentials ranging from 605–885 mV vs. NHE, under acidic aqueous conditions (1 M H2SO4). Four of the quinones are examined as cathodic electrolytes in an aqueous RFB, paired with anthraquinone-2,7-disulfonate (AQDS) as the anodic electrolyte. The RFB data complement the solution stability measures and show that the most stable electrolyte is a tetrasubstituted quinone containing four sulfonated thioether substituents. The results highlight the importance of substituting all C–H positions of the quinone in order to maximize the quinone stability and set the stage for design of improve organic electrolytes for aqueous RFBs. The authors thank Joseph Fourie for assisting in the synthesis of compound 8. Financial support for this work was provided by the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences (SSS, TWR, JBG, CWA, YP), with supplemental contributions by the Wisconsin Alumni Research Foundation (WARF) through the WARF Accelerator Program (YQ and partial support for JBG, CWA, YP). NMR spectroscopy facilities were partially supported by the NSF (CHE-0342998 and CHE-1048642), a UW Madison Instructional Laboratory Modernization Award, and a gift from Paul J. and Margaret M. Bender.

aqueous flow batteries, quinones, organic, redox m↗

Regional Oil and gas Aerial Methane Synthesis model (Analytica) (ROAMS Analytica) v1.5.2

The Regional Oil and gas Aerial Methane Synthesis model (Analytica) is a tool to convert the results of wide-area, source-resolved aerial methane remote sensing surveys of oil and natural gas infrastructure in a given region into methane emissions inventories (estimates of the magnitude and breakdown of methane emissions from the surveyed infrastructure). This version is written in the Analytica programming language, and this version accompanies a correction in preparation for submission to Sherwin et al. 2024 (Nature). The tool leverages databases of source-resolved methane emissions detected in aerial surveys, aerial survey coverage information (which areas were measured and when), data summarizing surveyed oil and natural gas infrastructure and production (derived from third-party databases), as well as state-of-the-art mechanistic emissions simulation tools to characterize emissions too small for the aerial system to see. The regional methane emissions estimates produced by this tool are much more granular in both space and asset type than common satellite- or flux tower-based regional estimates. Unlike other tools for converting site-level measurements into regional emissions estimates, our unique geostatistical approach integrates aerially measured emissions with limited need for statistical extrapolation, which can be highly sensitive to modeler assumptions. As a result, ROAMS-based estimates of regional methane emissions from oil and gas activity are widely viewed as highly credible, as evidenced by the success of Dr. Sherwin's recent paper in Nature.

Sherwin, Evan [Lawrence Berkeley National Laborato↗

Materials and Approaches for Mitigation of SOFC Cathode Degradation in SOFC Power Systems

Perovskites such as doped lanthanum manganite and cobaltite have been used successfully as a cathode material in SOFC power systems operating between 700-1000°C. The electrodes, however, remain prone to degradation in presence of Cr containing gas atmosphere under systems operating conditions. Cathode in SOFCs is considered as one of the largest contributors of electrochemical performance degradations, leading to significant increase in ohmic and non-ohmic losses as well as interfacial compound formation. These degradations are mostly irreversible due to permanent changes to chemical and morphological alterations in the electrodes, resulting in the blockage of triple phase boundary (TPB) sites and decrease in oxygen reduction reactions (ORR). Fundamental mechanistic understanding has been developed to elucidate the reaction pathways of electrode poisoning in electronically conducting electrodes (LSM) as well as mixed ionic and electronically conducting electrodes (LSCF). The overall goal of this program has been identification and development of cost effective solutions to mitigate electrode degradations under “real world” systems operating conditions. The overall technological innovations and impact from this work are: The research provides an understanding of the degradation mechanism and cost-effective approaches for implementation in SOFC systems; Develop mitigation processes utilizing low cost getters using conventional synthesis and fabrication route; Develop tailored high surface area powders and coatings for high Cr capture capacity under systems operating conditions; >Developed computational models to understand mechanistic behavior; Experimentally measure rate of Cr evaporation from chromia and alumina forming alloys under SOFC operating conditions; Developed conditions to minimize Cr evaporation from balance-of-plant alloys; This innovation will support the development of getter platform to capture both intrinsic and extrinsic impurities present in air; and, Applications under wide operating temperature range (500-900°C) as well for wide high-temperature electrochemical systems (SOFC, SOEC, and OTM). The work has been successfully developed, validated experimentally and implemented. Successful technology transfer of this knowledge with industrial partners has been accomplished and the getters have been independently tested and validated under their systems operating conditions. The innovation will also find application in related high temperature electrochemical systems such as OTM and SOEC for the prevention of Cr assisted performance degradation. The proposed approach for Cr capture can also be applied to oxy-combustion and other advanced combustion techniques for the reduction of Cr vapor in the exhaust gas stream. This fundamental knowledge gained also has led to the path forward for developing advanced getters for capturing more than one contaminant in air.

01 COAL, LIGNITE, AND PEAT↗