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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Single-Molecule Chemical Reactions Unveiled in Molecular Junctions

Understanding chemical processes at the single-molecule scale represents the ultimate limit of analytical chemistry. Single-molecule detection techniques allow one to reveal the detailed dynamics and kinetics of a chemical reaction with unprecedented accuracy. It has also enabled the discoveries of new reaction pathways or intermediates/transition states that are inaccessible in conventional ensemble experiments, which is critical to elucidating their intrinsic mechanisms. Thanks to the rapid development of single-molecule junction (SMJ) techniques, detecting chemical reactions via monitoring the electrical current through single molecules has received an increasing amount of attention and has witnessed tremendous advances in recent years. Research efforts in this direction have opened a new route for probing chemical and physical processes with single-molecule precision. This review presents detailed advancements in probing single-molecule chemical reactions using SMJ techniques. We specifically highlight recent progress in investigating electric-field-driven reactions, reaction dynamics and kinetics, host–guest interactions, and redox reactions of different molecular systems. Finally, we discuss the potential of single-molecule detection using SMJs across various future applications.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2021

Redox-Induced Structural Reorganization Dictates Kinetics of Cobalt(III) Hydride Formation via Proton-Coupled Electron Transfer

Two-electron, one-proton reactions of a family of [CoCp(dxpe)(NCCH 3 )] 2+ complexes (Cp = cyclopentadienyl, dxpe = 1,2-bis(di(aryl/alkyl)phosphino)ethane) form the corresponding hydride species [HCoCp(dxpe)] + through a stepwise proton-coupled electron transfer process. For three [CoCp(dxpe)(NCCH 3 )] 2+ complexes (dxpe = dppe (1,2-bis(diphenylphosphino)ethane), depe (1,2-bis(diethylphosphino)ethane), and dcpe (1,2-bis(dicyclohexylphosphino)ethane)), peak shift analysis was employed to quantify apparent proton transfer rate constants from cyclic voltammograms recorded with acids ranging 22 pK a units. The apparent proton transfer rate constants correlate with the strength of the proton source for weak acids, but these apparent proton transfer rate constants curiously plateau (k pl ) as the reaction becomes increasingly exergonic. The absolute apparent proton transfer rate constants across both these regions correlate with the steric bulk of the chelating diphosphine ligand, with bulkier ligands leading to slower kinetics (k plateau,depe = 3.5 x 10 7 M -1 s -1 , k plateau,dppe = 1.7 x 10 7 M -1 s -1 , k plateau,dcpe = 7.1 x 10 4 M -1 s -1 ). Mechanistic studies were conducted to identify the cause of the aberrant $k_PT^{app}$–ΔpK a trends. When the deuterated acids are employed, deuterium incorporation in the Cp ring is observed, indicating protonation of the CoCp(dxpe) species to form the corresponding hydride proceeds via initial ligand protonation. Digital simulations of cyclic voltammograms show ligand loss accompanying initial reduction gates subsequent PCET activity at higher driving forces. Together, these experiments reveal the details of the reaction mechanism: reduction of the Co(III) species is followed by dissociation of the bound acetonitrile ligand, subsequent reduction of the unligated Co(II) species to form a Co(I) species is followed by protonation, which occurs at the Cp ring, followed by tautomerization to generate the stable Co(III)-hydride product [HCoCp(dxpe)] + . Analysis as a function of chelating disphosphine ligand, solvent, and acid strength reveals that the ligand dissociation equilibrium is directly influenced by the steric bulk of the phosphine ligands and gates protonation, giving rise to the plateau of apparent proton transfer rate constant with strong acids. The complexity of the reaction mechanism underpinning hydride formation, encompassing dynamic behavior of the entire ligand set, highlights the critical need to understand elementary reaction steps in proton-coupled electron transfer reactions.

14 SOLAR ENERGY↗
DOE OSTI2022

Rewiring yeast metabolism for producing 2,3-butanediol and two downstream applications: Techno-economic analysis and life cycle assessment of methyl ethyl ketone (MEK) and agricultural biostimulant production

Rising concerns for sustainability and global climate change have driven the development of sustainable pro- duction pathways for biofuels and chemicals from lignocellulosic biomass via integrated biological and chemical processes. We constructed an engineered Saccharomyces cerevisiae capable of producing 2,3-butanediol (2,3-BDO) from glucose without accumulating ethanol and glycerol, which hinder downstream processing of 2,3-BDO, through extensive metabolic reprogramming. Specifically, we introduced heterologous 2,3-BDO biosynthetic enzymes and deleted the major isozymes of ethanol and glycerol biosynthetic enzymes. In addition, we introduced an NAD + regenerating Pyruvate-Malate (PM) cycle and enhanced the NAD + regenerating capability of the PM cycle to resolve the redox imbalance from the deletion of ethanol and glycerol production pathways. The resulting engineered yeast produced 109.9 g/L of 2,3-BDO with a productivity of 1.0 g/L/h and a yield of 0.36 g/ g glucose in a fed-batch fermentation. We also conducted techno-economic analysis (TEA) and life cycle assessment (LCA) of the production of methyl ethyl ketone (MEK) through catalytic dehydration of 2,3-BDO. A TEA based on the experimental results indicated that the minimum product selling price (MPSP) was estimated to be $1.90/kg. Regarding cradle-to-grave LCA, 100-year global warming potential (GWP100) and fossil energy consumption (FEC) were found to be 0.37 kg CO 2 eq/kg and 3.1 MJ/kg, respectively. These results demonstrated the feasibility of cost-competitive and sustainable bio-based MEK production via yeast fermentation. In addition, we explored the possibility of using the fermentation broth containing 2,3-BDO as a biostimulant inducing drought tolerance in plants. As a result, the yeast 2,3-BDO fermentation broth can induce drought tolerance in Arabidopsis thaliana without a complicated purification process.

2,3-butanediol (2,3-BDO)↗
DOE OSTI2022

A three-dimensional pore-scale model for redox flow battery electrode design analysis

A three-dimensional (3-D) pore-scale model has been developed to construct multiscale fibrous electrodes for redox flow batteries (RFB). New designs, such as biporous electrodes modify electrode structures by creating secondary pores on single carbon fiber to reduce internal battery resistance. Existing pore-scale models only resolve electrodes to the single carbon fiber scale and cannot incorporate recent multiscale electrode designs into numerical models. Our new model aims to bridge this gap and provide a tool to rapidly screen new electrode configurations. Two multiscale electrodes, laser-perforated and biporous electrodes, were investigated at varying operation conditions with the proposed 3-D pore-scale models. The laser-perforated electrode exhibits a reduced pressure drop, but follows the same permeability correlation compared to the corresponding pristine electrode. For the biporous electrode, the added specific surface area and faster reaction kinetics from the secondary pores are the most influential factors leading to improved battery efficiency. However, operating the biporous electrode in limiting current density conditions should be avoided due to the decreased mass transfer efficiency and a more significant voltage loss. Finally, we believe that our 3-D pore-scale model can accelerate the flow battery electrode design process and provide new insights into electrode geometry optimizations.

25 ENERGY STORAGE↗
DOE OSTI2020

A Novel NASICON‐Type Na 4 MnCr(PO 4 ) 3 Demonstrating the Energy Density Record of Phosphate Cathodes for Sodium‐Ion Batteries

Abstract Sodium‐ion batteries (SIBs) have attracted incremental attention as a promising candidate for grid‐scale energy‐storage applications. To meet practical requirements, searching for new cathode materials with high energy density is of great importance. Herein, a novel Na superionic conductor (NASICON)‐type Na 4 MnCr(PO 4 ) 3 is developed as a high‐energy cathode for SIBs. The Na 4 MnCr(PO 4 ) 3 nanoparticles homogeneously embedded in a carbon matrix can present an extraordinary reversible capacity of 160.5 mA h g −1 with three‐electron reaction at ≈3.53 V during the Na + extraction/insertion process, realizing an unprecedentedly high energy density of 566.5 Wh kg −1 in the phosphate cathodes for SIBs. It is intriguing to reveal the underlying mechanism of the unique Mn 2+ /Mn 3+ , Mn 3+ /Mn 4+ , and Cr 3+ /Cr 4+ redox couples via X‐ray absorption near‐edge structure spectroscopy. The whole electrochemical reaction undergoes highly reversible single‐phase and biphasic transitions with a moderate volume change of 7.7% through in situ X‐ray diffraction and ex situ high‐energy synchrotron X‐ray diffraction. Combining density functional theory (DFT) calculations with the galvanostatic intermittent titration technique, the superior performance is ascribed to the low ionic‐migration energy barrier and desirable Na‐ion diffusion kinetics. The present work can offer a new insight into the design of multielectron‐reaction cathode materials for SIBs.

Zhang, Jian↗
DOE OSTI2019

1.3 V superwide potential window sponsored by Na-Mn-O plates as cathodes towards aqueous rechargeable sodium-ion batteries

Aqueous rechargeable sodium-ion batteries (ARSIBs) are highly desirable for the large-scale energy storage due to their inherent high safety and low-cost. Na-Mn-O electrode material has been considered as a promising cathode, yet the redox potential window is still not fully explored and utilized in aqueous rechargeable sodium-ion batteries. Herein, a chemical bonded Na 0.44 MnO 2 (NMO) plates are successfully synthesized via a polyvinylpyrrolidone-assisted sol-gel route followed by annealing process. The possibility of utilizing a wider potential window ranging between –0.3 V and 1.0 V vs. Ag/AgCl in mild aqueous electrolyte has been thus demonstrated by using NMO plates as cathodes for the first time. As a result, the as-synthesized NMO plates can deliver a highest initial discharge capacity of 77.2 mA h g –1 at a current density of 100 mA g –1 , compared with previous Na-Mn-O reports in mild aqueous electrolyte in ARSIBs. Even at a high rate of 500 mA g –1 , it still maintains a large capacity of 35 mA h g –1 after 1000 cycles, demonstrating its superior cycling stability. In addition, ex situ SEM and TEM-EDX results reveal that there is a newly formed sheet-like layer Na-birnessite Na 0.55 Mn 2 O 4 · 1.5H 2 O on the surface of NMO cathodes, which can provide extra ion channel for sodium ions and stabilize the electrode from pulverization, resulting in improved cycling stability. Furthermore, this study provides a broad implication for developing low-cost, high performance cathode materials to broaden the applied potential window towards high performance ARSIBs.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Distribution of Mn Oxidation States in Grassland Soils and Their Relationships with Soil Pores

Manganese (Mn) is known to be an active contributor to processing and cycling of soil organic carbon (C), yet the exact mechanisms behind its interactions with C are poorly understood. Plant diversity in terrestrial ecosystems drives feedback links between plant C inputs and soil pores, where the latter, in turn, impact the redox environment and Mn. This study examined associations between soil pores (>36 μm Ø) and Mn within intact soils from two grassland ecosystems, after their >6-year implementation in a replicated field experiment. In this work, we used μ-XRF imaging and XANES spectroscopy to explore spatial distribution patterns of Mn oxidation states, combined with X-ray computed microtomography and 2D zymography. A high plant diversity system (restored prairie) increased soil C and modified spatial distribution patterns of soil pores as compared to a single species system (monoculture switchgrass). In switchgrass, the abundance of oxidized and reduced Mn oxidation states varied with distance from pores consistently with anticipated O 2 diffusion, while in the soil from restored prairie, the spatial patterns suggested that biological activity played a greater role in influencing Mn distributions. Based on the findings, we propose a hypothesis that Mn transformations promote C gains in soils of high plant diversity grasslands.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2019

Using Transient FTIR Spectroscopy to Probe Active Sites and Reaction Intermediates for Selective Catalytic Reduction of NO on Cu/SSZ-13 Catalysts

A Cu/SSZ-13 catalyst containing predominately Z2Cu sites is prepared. Using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), two non-steady state measurements, (1) continuous NO titration of an NH3 saturated catalyst and (2) intermittent NO on/off during quasi-steady state (i.e., NO perturbation), are conducted to shed light on active sites, reaction intermediates, and possible reaction mechanisms. During continuous NO titration, a strong NH3 inhibition effect is found, where Cu active sites containing NH3 ligands are less active than Cu sites depleted of NH3 ligands. In the NO perturbation experiments, it is demonstrated that NO+NH3 interactions lead to formation of Brønsted acid sites, which further interact with NH3 to form NH4+. Such a finding is fully consistent with a redox SCR mechanism proposed recently (Angew. Chem. Int. Ed. 2014, 53, 11828–11833). Perturbation measurements, using ND3 to replace NH3 in order to distinguish ammonia and nitrate vibrations, further show that NH4NO3 and other surface nitrates are not involved in the SCR process under typical low temperature quasi-steady state conditions. This work was financially supported by the national key research and development program of China (2017YFC0211302 and 2017YFC0211003), the Sino Japanese cooperation project (2016YFE0126600) and the China Postdoctoral Science Foundation (2017M620800). FG and CHFP gratefully acknowledge financial support for their participation from the US Department of Energy (DOE), Energy Efficiency and Renewable Energy, Vehicle Technologies Office. A portion of this work was performed in the Environmental Molecular Sciences Laboratory (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 for the US DOE by Battelle.

Cu, SSZ-13, SCR, DRIFTS, transient kinetics, mecha↗
DOE OSTI2020

NREL's Capabilities in Organism Development and Fermentation Sciences Research and Development (R&D)

NREL is developing robust microbial strains and scalable fermentation technologies for converting biomass sugars to fuels and biochemicals, and one-carbon (C1) gaseous substrates (e.g., CO2, CO, CH4) to high-value products. Core capabilities include: (1) Fermentation optimization of aerobic, microaerophilic, and anaerobic cultivation processes of gas and traditional liquid fermentation R&D; (2) Gas mass transfer R&D and CFD modeling for improved reactor design and gas mixing (3) Metabolic engineering in CRISPR editing tools to improve titer, rates, and yields; (4) Probing and optimizing carbon, redox, and energy flux using transcriptomics and fluxomic techniques; and (5) Consolidated bioprocessing (CBP) using cellulose and hemicellulose directly to minimize pretreatment.

BASIC BIOLOGICAL SCIENCES,BIOMASS FUELS,SYNTHETIC ↗
DOE OSTI2019

250 kWth Pilot Testing in Support of a 10 MWe Coal-Direct Chemical Looping Demonstration Feasibility Study

The Coal-Direct Chemical Looping (CDCL) process is emerging as a promising technology capable of high efficiency for producing electricity with low cost for carbon capture. In the CDCL process, coal is fully combusted to form carbon dioxide (CO2) and water via reaction with Fe2O3-based oxygen-carrier particles in a moving-bed reducer reactor. During reaction with coal, the Fe2O3 is reduced to form a mixture of Fe and FeO. The reduced particles are then transported to the combustor reactor where they are re-oxidized with air. The oxidation of the Fe and FeO mixture generates heat that can be used to produce steam for power generation. Once the particles are fully regenerated, they are pneumatically recycled to the reducer reactor where another reduction-oxidation (Redox) cycle begins. The Babcock & Wilcox Company (B&W) and The Ohio State University (OSU) have been developing the CDCL technology based on iron-based metal oxide particles circulating in a moving-bed reducer coupled with an entrained-flow combustor. As part of a Phase I effort of a DOE-sponsored project, B&W identified scale-up technology gaps for the coal-direct chemical looping reactor process, most of which fall under the moving-bed reactor design and operation. However, after the Phase I research, B&W concluded that the CDCL technology has the potential of generating electricity while meeting the DOE goals of greater than 90% CO2 capture and less than 35% increase in levelized cost of electricity (LCOE). B&W then moved to a Phase II project to design, build and demonstrate the CDCL technology at a 250 kWth capacity. B&W finished the construction and commissioning of the pilot test facility in 2017. The approach used to design a 250 kWth pilot-scale CDCL facility to investigate the technology gaps is presented. Important lessons from the commissioning activities that would transfer to commercial plant start-up are also shared. The findings from the test program are being incorporated into a Pre-FEED study for a 10 MWe large pilot demonstration. Under a separately-funded heat integration project, B&W and OSU are developing a multiphase computational fluid dynamic model (MFIX) of the combustor to quantify heat transfer to embedded steam generation surface, utilizing pinch analysis (ASPEN Energy Analyzer) to identify potential improvements of the heat integration scheme, and developing an integrated dynamic model (ProTRAX) of the steam turbine coupled with the chemical looping process to identify potential start-up and transient operation issues. Under an advanced control system for optimizing operation, B&W is supporting OSU to install a rules-based optimizer (B&W’s FocalPoint) on their 25 kWt bench-scale facility on the OSU West Campus. Finally, B&W and OSU were recently selected to perform a Phase I Feasibility study to evaluate installation of the 10 MWe pilot at the Dover Power & Light Municipal Power Plant in Dover, Ohio. The feasibility study includes compiling an Environmental Information Volume and generating a cost estimate for the design, construction and commissioning of the plant as well as lining up commitments from potential project participants and funding contributors. Updates on each project will be presented. The status of the technology development will be discussed. We focus on the progress made to date towards closing the technology gaps under each project.

20 FOSSIL-FUELED POWER PLANTS↗
DOE OSTI2018

Update on Design of 10 MWe Iron-Based Coal Direct Chemical Looping Demonstration Plant

The Coal-Direct Chemical Looping (CDCL) process is emerging as a promising technology capable of high efficiency for producing electricity with low cost for carbon capture. In the CDCL process, coal is fully combusted to form carbon dioxide (CO2) and water via reaction with Fe2O3-based oxygen-carrier particles in a moving-bed reducer reactor. During reaction with coal, the Fe2O3 is reduced to form a mixture of Fe and FeO. The reduced particles are then transported to the combustor reactor where they are re-oxidized with air. The oxidation of the Fe and FeO mixture generates heat that can be used to produce steam for power generation. Once the particles are fully regenerated, they are pneumatically recycled to the reducer reactor where another reduction-oxidation (Redox) cycle begins. The Babcock & Wilcox Company (B&W) and The Ohio State University (OSU) have been developing the CDCL technology based on iron-based metal oxide particles circulating in a moving-bed reducer coupled with an entrained-flow combustor. As part of a Phase I effort of a DOE-sponsored project, B&W identified scale-up technology gaps for the coal-direct chemical looping reactor process, most of which fall under the moving-bed reactor design and operation. However, after the Phase I research, B&W concluded that the CDCL technology has the potential of generating electricity while meeting the DOE goals of greater than 90% CO2 capture and less than 35% increase in levelized cost of electricity (LCOE). B&W then moved to a Phase II project to design, build and demonstrate the CDCL technology at a 250 kWth capacity. B&W finished the construction and commissioning of the pilot test facility in 2017. The approach used to design a 250 kWth pilot-scale CDCL facility to investigate the technology gaps is presented. Important lessons from the commissioning activities that would transfer to commercial plant start-up are also shared. The findings from the test program are being incorporated into a Pre-FEED study for a 10 MWe large pilot demonstration. Under a separately-funded heat integration project, B&W and OSU are developing a multiphase computational fluid dynamic model (MFIX) of the combustor to quantify heat transfer to embedded steam generation surface, utilizing pinch analysis (ASPEN Energy Analyzer) to identify potential improvements of the heat integration scheme, and developing an integrated dynamic model (ProTRAX) of the steam turbine coupled with the chemical looping process to identify potential start-up and transient operation issues. Under an advanced control system for optimizing operation, B&W is supporting OSU to install a rules-based optimizer (B&W’s FocalPoint) on their 25 kWt bench-scale facility on the OSU West Campus. Finally, B&W and OSU were recently selected to perform a Phase I Feasibility study to evaluate installation of the 10 MWe pilot at the Dover Power & Light Municipal Power Plant in Dover, Ohio. The feasibility study includes compiling an Environmental Information Volume and generating a cost estimate for the design, construction and commissioning of the plant as well as lining up commitments from potential project participants and funding contributors. Updates on each project will be presented. The status of the technology development will be discussed. We focus on the progress made to date towards closing the technology gaps under each project.

20 FOSSIL-FUELED POWER PLANTS↗
DOE OSTI2018

Gold core/ceria shell-based redox active nanozyme mimicking the biological multienzyme complex phenomenon

Catalytically active individual gold (Au) and cerium oxide (CeO2) nanoparticles are well known to exhibit specific enzyme-like activities, such as natural catalase, oxidase, superoxide dismutase, and peroxidase enzymes. These activities have been maneuvered to design several biological applications such as immunoassays, glucose detection, radiation and free radical protection and tissue engineering. A functional nanozyme depicting multienzyme like properties that functions as a synthetic super enzyme has eluded the researchers in the nanoscience community for past decade. In current report, we have designed a functional multienzyme in the form of Gold (core)-CeO2 (shell) nanoparticles (Au@CeO2 CSNPs) exhibiting excellent peroxidase, catalase and superoxide dismutase enzyme-like activities that are controlled simply by tuning the pH. The reaction kinetic parameters reveal that the peroxidase-like activity of this core shell nanozyme is comparable to natural HRP enzyme. Unlike peroxidase-like activity exhibited by other nanomaterials, Au@CeO2 CSNPs showed decrease in hydroxyl radical formation, suggesting that the bio catalytic reactions are performed by efficient electron transfers. A significant enzyme-like activity of this core shell nanoparticle was conserved at extreme pH (2 – 11) and temperatures (up to 90 °C), clearly suggesting the superiority over natural enzymes. Further, the utility of peroxidase-like activity of this core shell nanoparticles was extended for the detection of glucose, which showed a linear range of detection between (100 µM – 1 mM). It is hypothesized that the proximity of the redox potentials of Au+/Au and Ce (III)/Ce (IV) may result in a redox couple promoting the multienzyme activity of core shell nanoparticles. Au@CeO2 CSNPs may open new directions for development of single platform sensors in multiple biosensing applications.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2018

Effects of redox-active interlayer anions on the oxygen evolution reactivity of NiFe-layered double hydroxide nanosheets

Nickel-iron layered double hydroxide (NiFe-LDH) nanosheets have shown optimal oxygen evolution reaction (OER) performance; however, the role of the intercalated ions in the OER activity remains unclear. In this work, we show that the activity of the NiFe-LDHs can be tailored by the intercalated anions with different redox potentials. The intercalation of anions with low redox potential (high reducing ability), such as hypophosphites, leads to NiFe-LDHs with low OER overpotential of 240 mV and a small Tafel slope of 36.9 mV/dec, whereas NiFe-LDHs intercalated with anions of high redox potential (low reducing ability), such as fluorion, show a high overpotential of 370 mV and a Tafel slope of 80.8 mV/dec. The OER activity shows a surprising linear correlation with the standard redox potential. Density functional theory calculations and X-ray photoelectron spectroscopy analysis indicate that the intercalated anions alter the electronic structure of metal atoms which exposed at the surface. Anions with low standard redox potential and strong reducing ability transfer more electrons to the hydroxide layers. Finally, this increases the electron density of the surface metal sites and stabilizes their high-valence states, whose formation is known as the critical step prior to the OER process.

36 MATERIALS SCIENCE↗
DOE OSTI2020

In-situ/operando X-ray absorption spectroscopic investigation of the electrode/electrolyte interface on the molecular scale

A method for performing X-ray absorption spectroscopy (XAS) in the soft X-ray region was developed to investigate the surface-sensitive electron signal of electrode/electrolyte interfaces in common multivalent based organic solvents under in situ/operando conditions. Our approach enables us to probe the molecular-scale structure of electrode interfaces by measuring total electron yield and is suitable for redox systems exhibiting low intrinsic electrochemical current. In-situ F K-edge XAS measurements in a 0.5 M Magnesium bis(trifluoromethanesulfonimide)/2-Methyltetrahydrofuran (Mg(TFSI) 2 /2-MeTHF) electrolyte were carried out to determine the evolution of interfacial species during the electrochemical charging/discharging process. Time-dependent density-functional theory (TD-DFT) simulation indicate that the F K-edge evolution is the result of interfacial chemical environment change driven by electrochemical potential. In addition, we performed the “operando XAS” which runs the CV and collects spectra simultaneously. Furthermore, by using this method, the non-equilibrium state of condensed matter interfaces and interfacial dynamical transient process can be revealed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Thiol- and Disulfide-Functionalized Polycyclooctene: Metathesis Polymerization, Degradation, and Reformation

The enormous global production and use of polymers and plastics, combined with slower and less efficient disposal and recycling methods, have led to a worldwide growth in plastic waste. Here, we describe an approach that builds degradability into macromolecular polyolefins through the design of telechelic oligomers with reactive functional groups that enables control over polymer deconstruction and reconstruction. Our work exploits disulfide-containing polymers that have emerged as promising cyclable materials due to their dynamic reversibility (bond formation and cleavage) driven by redox chemistry under mild conditions. Specifically, we describe the synthesis of a telechelic α,ω-dithiopolycyclooctene (PCOE) by ring-opening metathesis polymerization using a dithioacetate chain transfer agent, followed by deprotection to convert the chain-end thioacetates to thiols. This process was studied towards control over the degree of oxidation to yield disulfide-containing PCOE, followed by an evaluation of reductive degradation and oxidative repolymerization. Overall, this approach facilitates the production of disulfide-containing unsaturated polyolefins and the integration of degradable and reformable moieties into soluble, processable, metathesis-derived polymers.

Lee, Kyoungwon↗
DOE OSTI2025

Electrochemically in situ formed rocksalt phase in titanium dioxide determines pseudocapacitive sodium-ion storage

Earth-abundant TiO 2 is a promising negative electrode for low-cost sodium-ion batteries (SIBs) owing to its high capacity, rapid (dis)charging capability, safe operation potential and nonflammability. Crystalline anatase TiO 2 is not suitable for reversible Na + (de)intercalation, but it displays pseudocapacitive response after repeated cycles. Herein, we find and demonstrate that ordered rocksalt (RS) NaTiO 2 nanograins are in situ formed by electrochemically cycling with Na + ions in anatase and amorphous TiO 2 . The in situ formed RS-NaTiO 2 follows a solid-solution reaction with small volume changes of only 2.0%, that determines the pseudocapacitive “mirror-like” cyclic voltammetry curve with a couple of broad redox peaks at 0.75 V vs. Na + /Na, a high capacity of 253 mAh g −1 , high-rate capability and thousands of stable cycles. The multistep crystalline-to-amorphous-to-RS transformations are able to be electrochemically activated during the aging process of assembled full cells. Our finding provides a direction for developing unconventional Ti-based high-performance active materials for SIBs with both high energy and power densities.

Tang, Dafu [Xiamen University (China); Innovation ↗
NASA NTRS2019

Aqueous Alteration on Mars

The occurrence of extensive valley networks and layered deposits of phyllosilicates and sulfates during the late Noachian/Hesperian periods (approx. 3-4 Gyrs) indicates a past martian climate that was capable of maintaining liquid water at the surface. The planet’s climate drastically changed after these early “episodes” of water to a drier and colder environment during the Amazonian period (past 3.0 Gyrs). The objective of this paper is to describe aqueous alteration/weathering scenarios on Mars based on observations returned by rover and lander missions. The chemistry of most outcrops, rocks, and “soils” that have interacted with water has not been extensively changed from average Mars crustal basaltic composition. Little chemical variation suggests closed hydrologic systems were prominent on early Mars and/or the water/rock ratios were low. Open hydrologic systems occur at local scales, e.g., high Si and Ti rocks and “soil” deposits around a volcanic feature in Gusev crater. Geochemical and mineralogical indicators for aqueous alteration include jarosite and other Fe-sulfates at several locations suggesting acid-sulfate alteration conditions. High Si and Ti rocks, sediments, and “soil” deposits are consistent with basaltic residues extenively leached by extremely acidic fluids. Variations in the Fe/Mn ratio of fracture veins infilled with sulfate-rich materials suggest changes in redox and/or pH conditions of the migrating fluids. The increase of nanophase iron oxides and salts with depth in several “soil” pits escavated by the Spirit rover’s wheel in Gusev crater suggests the translocation/mobolization of these phases by liquid water. This “pedogenic” process is the result of limited water movement through the surface sediments during the Amazonian period; however, it is likely that paleosols exist on Mars that formed during the early “wetter” history of the planet. Soil scientists have the opportunity to continue to (and should) be involved in the exploration of the Red planet.

Ming, Douglas W.↗
DOE OSTI2023

Data, figures, animations, and scripts associated with the manuscript "Integrated Effects of Site Hydrology and Vegetation on Exchange Fluxes and Carbon Cycling at the Coastal Terrestrial Aquatic Interface"

This package contains the data, figures, animations, and scripts used in "Integrated Effects of Site Hydrology and Vegetation on Exchange Fluxes and Carbon Cycling at the Coastal Terrestrial Aquatic Interface" (Li et al., 2023). This study examines the interactions between soil, vegetation and hydrologic conditions in coastal areas, with a focus on the Chesapeake Bay region. The researchers used a mechanistic model called ATS-PFLOTRAN to explore how these interactions affect exchange process in different regions and the carbon/nitrogen cycle across the terrestrial-aquatic interface (TAI). Simulation scenarios isolate the effects of control factors and reaction constants derived from laboratory experiments. The results show a carbon cycle "hot zone" in coastal wetlands and in the transition zone between wetlands and uplands. Transpiration enhances fluxes between the surface and subsurface domains and increases dissolved oxygen in TAI. The decomposition of leaf-derived organic carbon provides an additional source of carbon for aerobic respiration and denitrification in the TAI. Microbial activity plays a key role in controlling redox conditions and their variability. This modeling study improves the understanding of complex TAI interactions and facilitates the representation of coastal ecosystems in larger-scale Earth system models.Several files can be found from this data package.1. Readme,md: This file describe the Title, Target Journal, Target submission date, Co-author, Science Questions, Hypotheses, Key words, Key message, Model and Data, Repo Structure. The user can read this file first and then go to details.2. mesh.zip: This file contains the mesh file for simulation cases. 3. Figure.zip: This file contains figures used in the manuscript . 4. animation.zip: This file contains animations used in the manuscript . 5. Data.zip: This file contains all required input data, such as concentration and flow boundaries. Also, it contains the DEM and processes results on area fraction. 6. Simulation_setup_and_results.zip: This file contains setup of cases used in the manuscript . The result files are too large, if you need that data, please contact to the Author. 7. notebooks.zip: This file contains the Jupyter notebooks for performing sensitivity analysis and other pre-process and post-process analyses.

54 ENVIRONMENTAL SCIENCES↗