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DOE OSTI2024

Development of Electrolytes under Lean Condition in Lithium–Sulfur Batteries

Lithium–sulfur (Li–S) batteries stand out as one of the promising candidates for next-generation electrochemical energy storage technologies. A key requirement to realize high-specific-energy Li–S batteries is to implement low amount of electrolyte, often characterized by the electrolyte/sulfur (E/S) ratio. Low E/S ratio aggravates the known challenges for Li–S batteries and introduces new ones originated from the high concentration of polysulfides in limited electrolyte reservoir. Here, in this review, the connections between the fundamental properties of electrolytes and the electrochemical/chemical reactions in Li–S batteries under lean electrolyte condition are elucidated. The emphasis is on how the solvating properties of the electrolyte affect the fate of polysulfides. Built upon the mechanistic analysis, different strategies to design lean electrolytes to improve the overall process of Li–S reactions and Li anode protection are discussed.

25 ENERGY STORAGE↗

DOE OSTI2023

Asynchronous domain dynamics and equilibration in layered oxide battery cathode

To improve lithium-ion battery technology, it is essential to probe and comprehend the microscopic dynamic processes that occur in a real-world composite electrode under operating conditions. The primary and secondary particles are the structural building blocks of battery cathode electrodes. Their dynamic inconsistency has profound but not well-understood impacts. In this research, we combine operando coherent multi-crystal diffraction and optical microscopy to examine the chemical dynamics in local domains of layered oxide cathode. Our results not only pinpoint the asynchronicity of the lithium (de)intercalation at the sub-particle level, but also reveal sophisticated diffusion kinetics and reaction patterns, involving various localized processes, e.g., chemical onset, reaction front propagation, domains equilibration, particle deformation and motion. These observations shed new lights onto the activation and degradation mechanisms of state-of-the-art battery cathode materials.

25 ENERGY STORAGE↗

DOE OSTI2021

Impact of KOH on the interfacial precipitation rates of C-S-H during the early hydration of C3S

In this work we investigated the influence of alkalis on the hydration of two triclinic samples of C{sub 3}S. One pure C{sub 3}S and one Al-doped C{sub 3}S (0.5 wt.‐% Al{sub 2}O{sub 3}). We added differently concentrated KOH solutions representing alkalis in the pore solution, which lead to an increase of the interfacial precipitation rates of C-S-H during the hydration of C{sub 3}S compared to the hydration without KOH. Isothermal calorimetry was conducted for the determination of the rates of reaction during the hydration process and ICP-OES measurements for the determination of the pore solution composition at certain times of hydration. The increasing effect of KOH solution on the calculated interfacial precipitation rates from pore solution data can explain the enhancement of the rates of reaction recorded by heat flow calorimetry during the early hydration. Therefore, the interfacial precipitation rates of C-S-H can accurately describe the acceleration effect of alkalis on the early hydration of C{sub 3}S.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Imine Reductase-Catalyzed, Radical-Mediated Asymmetric Cyano Group Migration

Functional group migration (FGM) reactions represent a fundamental class of transformations in organic chemistry, enabling the repositioning of functional moieties in nonobvious ways. However, catalytic asymmetric radical-mediated FGMs remain rare due to the inherent challenges of achieving catalyst-controlled enantioselectivity over free radical intermediates. Herein, we repurpose imine reductases (IREDs), a class of biotechnologically important enzymes known for their substrate promiscuity, to enable the first examples of catalytic asymmetric cyano group migration via a radical mechanism. An orthogonal set of radical enzymes, including PbaIREDCym and SmiIREDCym, was engineered, allowing both 1,4- and 1,5-cyano group migration reactions to occur in an enantiodivergent fashion. The use of the nonionic surfactant TPGS-1000 was found to improve both the yield and enantioselectivity of these cyano migration reactions. Furthermore, this biocatalytic process exhibited a broad substrate scope and is readily scalable, affording a rare example of chiral nonamine product assembly with imine reductases. More broadly, stereoselective radical biocatalysis with engineered IREDs and other versatile enzymes provides a potentially general solution to challenging asymmetric FGM reactions.

Biocatalysis↗

DOE OSTI2021

Real-time visualization of particle evolution during reactive flux-assisted processing of aluminum melts

Here, a multi-modal, multi-scale correlative tomography investigation of Al-TiC metal matrix composites processed via flux-assisted reaction synthesis is reported. Synchrotron X-ray microradiography is utilized to visualize the reaction and particle evolution in real-time. Changes in particle diameter and areal number density suggest that the process is nucleation- rather than growth-dominated. At 950 °C, the bulk of the reaction takes place in a relatively short time span of less than 600 s. The microstructure is imaged at higher resolution in 2D (scanning electron microscopy) and 3D (synchrotron X-ray nanotomography), revealing the formation of carbide particles with a hexagonal platelet morphology. We propose that the morphology arises due to the incorporation of Si impurities during the experiment. It is expected that the correlative tomography workflow and analysis may guide future metal matrix composite (MMC) processing strategies.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Bond Selective Photochemistry at Metal Nanoparticle Surfaces: CO Desorption from Pt and Pd

The use of visible photon fluxes to influence catalytic reactions on metal nanoparticle surfaces has attracted attention based on observations of reaction mechanisms and selectivity not observed under equilibrium heating. These observations suggest that photon fluxes can selectively impact the rates of certain elementary steps, creating nonequilibrium energy distributions among various reaction pathways. However, quantitative studies validating these hypotheses on metal nanoparticle surfaces are lacking. Here, we examine the influence of continuous wave visible photon fluxes on the CO desorption rates from 1 to 2 nm diameter Pt and Pd nanoparticle surfaces supported on γ-Al 2 O 3 . Temperature-programmed desorption measurements quantified via diffuse reflectance infrared Fourier transform spectroscopy demonstrate that visible photon fluxes significantly enhanced the rate of CO desorption from Pt nanoparticles in a wavelength-dependent manner. 440 nm photons most efficiently promoted CO desorption from Pt nanoparticle surfaces, aligning with the excitation energy for the interfacial electronic transition within the Pt–CO bond. Conversely, visible photon fluxes had no measurable influence on CO desorption rates from Pd nanoparticle surfaces after accounting for photon-induced heating. Density functional theory calculations demonstrate that the Pt–CO bond exhibits a narrower LUMO resonance, stronger coupling between the photoexcitation and forces induced on the metal–C bond, and vibrational energy dissipation that more effectively couples to desorption as compared to Pd–CO. These results demonstrate the specificity photons provide in facilitating chemical reactions on metal nanoparticle surfaces and substantiate the idea that photon fluxes can steer processes and outcomes of catalytic reactions in ways not achievable by equilibrium heating.

desorption↗

DOE OSTI2023

Summertime ozone pollution in China affected by stratospheric quasi-biennial oscillation

In recent years, the near-surface ozone (O 3 ) level has been rising fast in China, with increasing damage to human health and ecosystems. In this study, the impact of stratospheric quasi-biennial oscillation (QBO) on interannual variations in summertime tropospheric O 3 over China is investigated based on GEOS-Chem model simulations and satellite retrievals. QBO has a significant positive correlation with near-surface O 3 concentrations over central China (92.5–112.5° E, 26–38° N) when the sea surface temperature (SST) over the eastern tropical Pacific is warmer than normal, with a correlation coefficient of 0.53, but QBO has no significant effect on O 3 under the cold SST anomaly. Compared to the easterly phase of QBO, the near-surface O 3 concentrations have an increase of up to 3 ppb (5% relative to the average) over central China during its westerly phase under the warm SST anomaly. O 3 also increases above the surface and up to the upper troposphere, with a maximum increase of 2–3 ppb (3%–5%) in 850–500 hPa over central China when comparing westerly phase to easterly phase. Process-based analysis and sensitivity simulations suggest that the O 3 increase over central China is mainly attributed to the anomalous downward transport of O 3 during the westerly phase of QBO when a warm SST anomaly occurs in the eastern tropical Pacific, while the local chemical reactions and horizontal transport processes partly offset the O 3 increase. This work suggests a potentially important role of QBO and the related vertical transport process in affecting near-surface O 3 air quality, with an indication for O 3 pollution prediction and prevention.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI1961

Laboratory Development of a Pot Calcination Process for Converting Liquid Wastes to Solids

Simulated Darex, Purex, Thorex, and TBP-25 wastes were batch-evaporated and calcined to solids. The weight of residue was decreased to ~ 8% of the original waste for Darex, to ~ 4% for Purex, to ~ 2% for Thorex, and ~ 7% for TBP-25 by calcination to 1200°C. Semicontinuous evaporation and calcination to solids at 900°C of Darex and Purex wastes gave volume reduction factors of ~ 8 and 7 to 10, respectively. The nitrate contents of the residues from batch calcination to 800°C were from ~ 0.07 to 0.5 wt % while the nitrate contents of the residues from semicontinuous calcination to 900°C were from ~ 0.1 to 0.7 wt %. Sodium, calcium, and magnesium additives to Purex waste decreased the percent of sulfate volatilized into the condensate from ~ 30% to <0.5%. Replacement of the atmosphere above the waste with nitric oxide decreased ruthenium volatility from 50 to 60% of that originally present in Purex waste to 0.5 to 3.5%. The thermal conductivities for the calcined wastes, measured in situ, were all >0.1 Btu/hr ft °F at ~ 400°F and increased almost linearly with increasing temperature to >0.3 Btu/hr ft °F at ~ 1600°F in all cases studied.

052001* -- Nuclear Fuels-- Waste Processing↗

DOE OSTI2025

Nuclear level density and γ -ray strength function of Ni 67 and the impact on the i process

Proton- γ coincidences from ( d , p ) reactions between a Ni 66 beam and a deuterated polyethylene target have been analyzed with the inverse-Oslo method to find the nuclear level density (NLD) and γ -ray strength function ( γ SF ) of Ni 67 . The Ni 66 ( n , γ ) capture cross section has been calculated using the Hauser-Feshbach model in using the measured NLD and γ SF as constraints. The results confirm that the Ni 66 ( n , γ ) reaction acts as a bottleneck when relying on one-zone nucleosynthesis calculations. However, the impact of this reaction is strongly dampened in multizone models of low-metallicity AGB stars experiencing i -process nucleosynthesis. Published by the American Physical Society 2025

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

DOE OSTI2021

BETO 2021 Peer Review - Catalytic Upgrading of Pyrolysis Vapors 2.3.1.314

Catalytic fast pyrolysis (CFP) is a versatile pathway for the direct liquefaction of biomass and waste carbon sources to generate a stabilized bio-oil intermediate that can be further processed into renewable fuels, chemicals, and materials. The objective of this project is advance the CFP state-of-technology through integrated catalyst and process development, expand market responsiveness by creating routes to novel co-products, and provide experimental data to inform process modelling and scale-up activities. Research advancements over the past two years include reducing analytical uncertainty by achieving 100 ± 1% carbon balances during reaction testing with woody biomass, improving process efficiency by achieving a 4x increase in catalyst cycle length, demonstrating compatibility with waste feedstocks, and confirming process durability for 100+ reaction cycles. Additionally, this project supported a comprehensive pathway review to evaluate scale-up needs. This review resulted in the early identification of technical risks and informed proactive planning for the BETO 2022 Verification. Other impacts from this project include generation of broadly enabling scientific knowledge (14 publications/18 presentations since 2019), engagement with industry partners (e.g., Johnson Matthey and ExxonMobil), and identification of a promising pathway to market that addresses emerging demands for biogenic refinery feedstocks.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

DOE OSTI2021

Methanol carbonylation to acetaldehyde on Au particles supported by single-layer MoS 2 grown on silica

Homogenous single-layer MoS 2 films coated with sub-single layer amounts of gold are found to isolate the reaction of methanol with carbon monoxide, the fundamental step toward higher alcohols, from an array of possible surface reactions. Active surfaces were prepared from homogenous single-layer MoS 2 films coated with sub-single layer amounts of gold. These gold atoms formed clusters on the MoS2 surface. A gas mixture of carbon monoxide (CO) and methanol (CH 3 OH) was partially converted to acetaldehyde (CH 3 CHO) under mild process conditions (308 kPa and 393 K). This carbonylation of methanol to a C 2 species is a critical step toward the formation of higher alcohols. Density functional theory modeling of critical steps of the catalytic process identify a viable reaction pathway. Imaging and spectroscopic methods revealed that the single layer of MoS 2 facilitated formation of nanoscale gold islands, which appear to sinter through Ostwald ripening. Here, the formation of acetaldehyde by the catalytic carbonylation of methanol over supported gold clusters is an important step toward realizing controlled production of useful molecules from low carbon-count precursors.

2D catalyst↗

DOE OSTI2022

Chemical and Electrochemical O 2 Reduction on Earth-Abundant M-N-C Catalysts and Implications for Mediated Electrolysis

M-N-C catalysts, incorporating non-precious-metal ions (e.g. M = Fe, Co) within a nitrogen-doped carbon support, have been the focus of broad interest for electrochemical O 2 reduction and aerobic oxidation reactions. The present study explores the mechanistic relationship between the O 2 reduction mechanism under electrochemical and chemical conditions. In this work, chemical O 2 reduction is investigated via the aerobic oxidation of a hydroquinone, in which the O–H bonds supply the protons and electrons needed for O 2 reduction to water. Mechanistic studies have been conducted to elucidate whether the M-N-C catalyst couples two independent half-reactions (IHR), similar to electrode-mediated processes, or mediates a direct inner-sphere reaction (ISR) between O 2 and the organic molecule. Kinetic data support the latter ISR pathway. This conclusion is reinforced by rate/potential correlations that reveal significantly different Tafel slopes, implicating different mechanisms for chemical and electrochemical O 2 reduction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Tracking the ultraviolet-induced photochemistry of thiophenone during and after ultrafast ring opening

Photoinduced isomerization reactions lie at the heart of many chemical processes in nature. The mechanisms of such reactions are determined by a delicate interplay of coupled electronic and nuclear dynamics occurring on the femtosecond scale, followed by the slower redistribution of energy into different vibrational degrees of freedom. In this study, we apply time-resolved photoelectron spectroscopy with a seeded extreme ultraviolet free-electron laser to trace the ultrafast ring opening of gas-phase thiophenone molecules following ultraviolet photoexcitation. When combined with ab initio electronic structure and molecular dynamics calculations of the excited- and ground-state molecules, the results provide insights into both the electronic and nuclear dynamics of this fundamental class of reactions. The initial ring opening and non-adiabatic coupling to the electronic ground state are shown to be driven by ballistic S–C bond extension and to be complete within 350 fs. Theory and experiment also enable visualization of the rich ground-state dynamics that involve the formation of, and interconversion between, ring-opened isomers and the cyclic structure, as well as fragmentation over much longer timescales.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Achieving high ethylene yield in non-oxidative ethane dehydrogenation

Steam cracking of ethane, a non-catalytic thermochemical process, remains the dominant means of ethylene production. The severe reaction conditions and energy expenditure involved in this process incentivize the search for alternative reaction pathways and reactor designs which maximize ethylene yield while minimizing cost and energy input. Herein, we report a comparison of catalytic and non-catalytic non-oxidative dehydrogenation of ethane. We achieve ethylene yields as high as 67 % with an open tube quartz reactor without the use of a catalyst at residence times ~4 s. The open tube reactor design promotes simplicity, low cost, and negligible coke formation. Pristine quartz tubes were most effective, since coke formation was detected when defects were introduced by scratching the surface of the quartz. Surprisingly, the addition of solids to the quartz tube, such as quartz sand, alumina powder, or even Pt-based intermetallic catalysts, led to lower ethylene yield. Pt alloy catalysts are effective at lower temperatures, such as at 575 °C, but conversion is limited due to thermodynamic constraints. When operated at industrially relevant temperatures, such as 700 °C and above, these catalysts were not stable in our tests, causing ethylene yield to drop below that of the open tube. Furthermore, these results suggest that future research on non-oxidative dehydrogenation should be directed at optimizing reactor designs to improve the conversion of ethane to ethylene, since this approach shows promise for decentralized production of ethylene from natural gas deposits.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Efficient low-temperature, catalyst-free dehydrogenation of alkanes

Riley, Christopher Ryan↗

DOE OSTI2019

Theoretical Calculation Guided Design of Single-Atom Catalysts toward Fast Kinetic and Long-Life Li–S Batteries

Lithium–sulfur (Li–S) batteries are enticing next-generation energy storage technologies due to their high theoretical energy density, environmental friendliness, and low cost. Yet, low conductivity of sulfur species, dissolution of polysulfides, poor conversion from sulfur reduction, and lithium sulfide (Li 2 S) oxidation reactions during discharge–charge processes hinder their practical applications. Herein, under the guidance of density functional theory calculations, we have successfully synthesized large-scale single atom vanadium catalysts seeded on graphene to achieve high sulfur content (80 wt % sulfur), fast kinetic (a capacity of 645 mAh g –1 at 3 C rate), and long-life Li–S batteries. Both forward (sulfur reduction) and reverse reactions (Li 2 S oxidation) are significantly improved by the single atom catalysts. This finding is confirmed by experimental results and consistent with theoretical calculations. The ability of single metal atoms to effectively trap the dissolved lithium polysulfides (LiPSs) and catalytically convert the LiPSs/Li 2 S during cycling significantly improved sulfur utilization, rate capability, and cycling life. Our work demonstrates an efficient design pathway for single atom catalysts and offers solutions for the development of high energy/power density Li–S batteries.

25 ENERGY STORAGE↗

DOE OSTI2025

Morphogenic Growth 3D Printing

Inspired by nature's morphogenesis, a new 3D printing process –growth printing (GP)– takes advantage of a self‐propagating curing front to produce 3D polymeric parts following a growth‐like development plan. The propagation of the curing front is driven by the exothermic polymerization of dicyclopentadiene (DCPD), which transforms the liquid resin into a stiff polymer as it propagates at 1 mm s −1 . GP is triggered when a heated initiator contacts the uncured liquid resin in an open container. The initiator nucleates the frontal polymerization reaction and the isotropic radial propagation of the growth front. Simultaneously, the initiator is moved up across the free surface of the resin, pulling the cured object out of the uncured resin. The motion trajectory of the initiator with respect to the free resin surface controls the growth morphology of the 3D part. An inverse design algorithm is developed to produce 3D parts by modeling the reaction‐diffusion‐driven solidification process. This process has substantial energy savings and high printing speeds.

3D printing↗

DOE OSTI2021

Ignition delay times of NH 3 /DME blends at high pressure and low DME fraction: RCM experiments and simulations

Here, autoignition delay times of ammonia/dimethyl ether (NH 3 /DME) mixtures were measured in a rapid compression machine with DME fractions of 0, 2 and 5 and 100% in the fuel. The measurements were performed at equivalence ratios $\varphi$= 0.5, 1.0 and 2.0 and pressures in the range 10–70 bar; depending on the fuel composition, the temperatures after compression varied from 610 K to 1180 K. Admixture of DME is seen to have a dramatic effect on the ignition delay time, effectively shifting the curves of ignition delay vs. temperature to lower temperatures, up to ~250 K compared to pure ammonia. Two-stage ignition is observed at $\varphi$= 1.0 and 2.0 with 2% and 5% DME in the fuel, despite the pressure being higher than that at which pure DME shows two-stage ignition. At $\varphi$= 0.5, a reproducible pre-ignition pressure rise is observed for both DME fractions, which is not observed in the pure fuel components. A novel NH 3 /DME mechanism was developed, including modifications in the NH 3 subset and addition of the NH 2 + CH 3 OCH 3 reaction, with rate coefficients calculated from ab initio theory. Simulations faithfully reproduce the observed pre- ignition pressure rise. While the mechanism also exhibits two-stage ignition for NH 3 /DME mixtures, both qualitative and quantitative improvement is recommended. The overall ignition delay times for ammonia/DME mixtures are predicted well, generally being within 50% of the experimental values, although reduced performance is observed for pure ammonia at $\varphi$= 2.0. Simulating the ignition process, we observe that the DME is oxidized much more rapidly than ammonia. Analysis of the mechanism indicates that this ‘early DME oxidation’ generates reactive species that initiate the oxidation of ammonia, which in turn begins heat release that raises the temperature and accelerates the oxidation process towards ignition. The reaction path analysis shows that the low-temperature chain-branching reactions of DME are important in the early oxidation of the fuel, while the sensitivity analysis indicates that several reactions in the oxidation of DME, including cross reactions between DME and NH 3 species presented here, are critical to ignition, even at fractions of 2% DME in the fuel.

10 SYNTHETIC FUELS↗