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Results for “Chemical Reaction Cycle”

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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At least 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Modular Electrochemical Synthesis Using a Redox Reservoir Paired with Independent Half-Reactions

Electrochemical synthesis of high-value chemicals using renewable electricity could lead to sustainability advantages over conventional chemical manufacturing. The tight coupling between paired anodic and cathodic reactions in conventional electrochemical processes, however, constrains the products and their efficiencies. Here, we demonstrate a strategy to achieve modular electrochemical synthesis (ModES) of different chemicals by decoupling and pairing the oxidative and reductive half-reactions with a heterogeneous redox reservoir (RR). Specifically, sodium nickel hexacyanoferrate (NaNiHCF) can serve as a robust and reversible RR that enables the modular production of several strong oxidants, hydrogen peroxide (H 2 O2) and sodium persulfate (Na 2 S 2 O 8 ) or active chlorine, in separate RR-coupled electrochemical processes. The system’s excellent performance and operational stability is demonstrated by continuous operation over 100 cycles (~36 h) to produce H 2 O 2 and Na 2 S 2 O 8 with a high voltage efficiency. The concept presented here highlights the prospects for using RRs to enable efficient, modular, and on-demand electrochemical synthesis of valuable chemicals.

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

Evolution and Degradation Patterns of Electrochemical Cells Based on the Analysis of Interfacial Phenomena at Li Metal Anode/Electrolyte Interfaces

In this work, we report the results of a theoretical–computational analysis of the solid electrolyte interphase (SEI) growth and degradation dynamics occurring in lithium metal batteries during cycling. We use ab initio-kinetic Monte Carlo simulations to generate a synthetic data set, which is analyzed by machine learning methods. We aim to determine: (i) how modifications in interfacial interaction energies between solid electrolyte interphase (SEI) blocks and between Li ions and SEI facets impact the Coulombic efficiency (CE) of the battery and (ii) what factors, including reactions, microscopic transport, and other interfacial events, may lead to cell performance “failure” during prolonged charge and discharge cycles, signaled as a sharp decay in the CE over cycling. The demonstration of our approach is done on a cell including a Li metal surface interfacing with a previously introduced state-of-the-art electrolyte, and the idea can be applied to any electrochemical system. Outcomes include the identification of the leading chemical, physical, and structural variables causing cell failure and relating them to the electrolyte formulation, thus paving the way to future more refined analysis and electrolyte design.

batteries↗
DOE OSTI2021

Towards chemical equilibrium in thermochemical water splitting. Part 1: Thermal reduction

The efficiency of many processes strongly depends on their thermodynamic reversibility, i.e., proximity to equilibrium throughout the process. In thermochemical cycles for water and/or carbon dioxide splitting, thermochemical air separation, and thermochemical energy storage, operating near equilibrium means that the oxygen chemical potential of the solid and gas phases must not differ significantly. Herein we show that approaching this ideal is possible in thermal reduction only if the reaction step occurs at a specific, reaction coordinate- and material-dependent temperature. The resulting thermal reduction temperature profile also depends on the ratio of gas and solid flows.

08 HYDROGEN↗
DOE OSTI2022

Mechanistic Insights on the Low-Temperature Oxidation of CO Catalyzed by Isolated Co Ions in N-Doped Carbon

Isolated cobalt ions on nitrogen-doped carbon (Co-N-C) catalyze CO oxidation at temperatures as low as 196 K, but the active site and mechanism for this reaction remain elusive. In this work, steady-state CO oxidation around 273 K over Co-N-C revealed nearly first order behavior in both CO and O 2 as well as a negative apparent activation energy. Isotopic transient analysis of the reaction confirmed a rapid turnover frequency and low surface coverage of adsorbed intermediates leading to CO 2 (< 10% of the Co). Results from kinetics experiments combined with quantum chemical calculations and molecular dynamics simulations are consistent with a reaction path involving weak adsorption of CO onto Co ions followed by a low barrier for the CO-assisted activation of weakly adsorbed O 2 . Furthermore, this proposed mechanism for dioxygen activation does not involve a redox cycle with the transition metal ion and may be important in other low temperature catalytic reactions involving O 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

The passivity of lithium electrodes in liquid electrolytes for secondary batteries

Rechargeable Li metal batteries are currently limited by electrolyte decomposition and rapid Li consumption. Li plating and stripping greatly depend on the solid electrolyte interphase formed at the Li metal-liquid electrolyte interface. This Review discusses the reactions occurring at this interface from a corrosion science perspective, highlighting the requirements for an ideal passivation layer. Rechargeable Li metal batteries are currently limited by safety concerns, continuous electrolyte decomposition and rapid consumption of Li. These issues are mainly related to reactions occurring at the Li metal-liquid electrolyte interface. Additionally, the formation of a passivation film (that is, a solid electrolyte interphase) determines ionic diffusion and the structural and morphological evolution of the Li metal electrode upon cycling. In this Review, we discuss spontaneous and operation-induced reactions at the Li metal-electrolyte interface from a corrosion science perspective. We highlight that the instantaneous formation of a thin protective film of corrosion products at the Li surface, which acts as a barrier to further chemical reactions with the electrolyte, precedes film reformation, which occurs during subsequent electrochemical stripping and plating of Li during battery operation. Finally, we discuss solutions to overcoming remaining challenges of Li metal batteries related to Li surface science, electrolyte chemistry, cell engineering and the intrinsic instability of the Li metal-electrolyte interface.

25 ENERGY STORAGE↗
DOE OSTI2022

The Role of Pulse Radiolysis in Advanced Nuclear Fuel Cycles

The effects of ionizing radiation are ubiquitous throughout all aspects of a nuclear fuel cycle. The complexity and intensity of these effects are greatest during reactor operations and in the management of used nuclear fuel and waste. Radiation-induced processes typically promote the chemical transformation of molecules and materials with the formation of potentially detrimental degradation products and corresponding changes in physical and chemical properties, which ultimately impact the effectiveness and longevity of nuclear technologies. Consequently, a molecular-level understanding of radiation effects over multiple time, distance, and material domains is essential for the innovation and deployment of next generation nuclear technologies. Attaining this knowledge necessitates a firm grasp of radiation-induced reaction kinetics, for which pulsed electron radiolysis is the methodology of choice. Presented here are several recent studies from our group that demonstrate the critical role of pulsed electron radiolysis techniques in the advancement of our understanding of radiation-induced chemistry under advanced nuclear fuel cycle conditions. Research topics include late actinide redox chemistry, radiation robustness of used nuclear fuel reprocessing complexants, and the behavior of metal cations in high temperature molten salt media.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2025

Hydrogel-Immobilized Multienzyme Systems for Cell-Free Chemical Bioproduction

Cell-free gene expression systems derived from bacterial lysates enable the expression of biosynthetic pathways from inexpensive and easily prepared DNA templates. These systems hold great promise for modular and on-demand bioproduction of valuable small molecules in resource-limited settings but are constrained in their long-term stability, reusability, and deployability. In this work, we demonstrate that multiple cell-free expressed enzymes can be co-immobilized in biocompatible hydrogels made from poly(ethylene glycol) diacrylate (PEGDA) with added glycerol for enhanced gel integrity. Using small-angle X-ray scattering (SAXS), we show that the mesh size of PEGDA-glycerol hydrogels is comparable to the globular sizes of many proteins and enzymes, which could be used for protein entrapment. We found that the combination between entrapment and chemical ligation of the enzymes was effective to retain proteins. By employing a method for direct fluorescence measurement from hydrogels, we found that proteins can be retained in PEGDA-glycerol for at least a week. By separating the cell-free enzyme expression from the immobilization step, we successfully fabricated enzyme-laden hydrogels with three heterologous cell-free enzymes for the bioconversion of pyruvic acid to malic acid, an industrially valuable and versatile precursor chemical. Both heterologous and endogenous enzymes from the lysate remain functional in photo-cross-linked hydrogels and can be reused for multiple biocatalytic cycles. Moreover, we also found that the immobilized enzymes exhibit up to 1.6-fold higher activity and 2-fold longer lifetimes than free enzymes in liquid reactions. Furthermore, these results could advance the deployment of cell-free synthetic biology because they show that reusable, stable, and durable multienzyme systems can be created using readily available materials and fabrication techniques.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Insights into interfacial effect and local lithium-ion transport in polycrystalline cathodes of solid-state batteries

Interfacial issues commonly exist in solid-state batteries, and the microstructural complexity combines with the chemical heterogeneity to govern the local interfacial chemistry. The conventional wisdom suggests that “point-to-point” ion diffusion at the interface determines the ion transport kinetics. Here, we show that solid-solid ion transport kinetics are not only impacted by the physical interfacial contact but are also closely associated with the interior local environments within polycrystalline particles. In spite of the initial discrete interfacial contact, solid-state batteries may still display homogeneous lithium-ion transportation owing to the chemical potential force to achieve an ionic-electronic equilibrium. Nevertheless, once the interior local environment within secondary particle is disrupted upon cycling, it triggers charge distribution from homogeneity to heterogeneity and leads to fast capacity fading. Our work highlights the importance of interior local environment within polycrystalline particles for electrochemical reactions in solid-state batteries and provides crucial insights into underlying mechanism in interfacial transport.

25 ENERGY STORAGE↗
DOE OSTI2020

Thermodynamic and kinetic hydricity of transition metal hydrides

The prevalence of transition metal-mediated hydride transfer reactions in chemical synthesis, catalysis, and biology has inspired the development of methods for characterizing the reactivity of transition metal hydride complexes. Thermodynamic hydricity represents the free energy required for heterolytic cleavage of the metal–hydride bond to release a free hydride ion, H - , as determined through equilibrium measurements and thermochemical cycles. Kinetic hydricity represents the rate of hydride transfer from one species to another, as measured through kinetic analysis. This tutorial review describes the common methods for experimental and computational determination of thermodynamic and kinetic hydricity, including advice on best practices and precautions to help avoid pitfalls. The influence of solvation on hydricity is emphasized, including opportunities and challenges arising from comparisons across several different solvents. Connections between thermodynamic and kinetic hydricity are discussed, and opportunities for utilizing these connections to rationally improve catalytic processes involving hydride transfer are highlighted.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Optimizing a chemical cleaning protocol to determine the nickel isotopic composition of ancient seawater from carbonates

Reconstructing the ancient marine cycle of Ni, a trace metal in the oceans essential to enzymes regulating the C, N, and O cycles, would inform how Ni bioavailability shaped early life. The Ni isotopic composition of seawater (δ 60 Ni SW ) through time could provide insight, but this approach requires sedimentary archives that faithfully record δ 60 Ni SW . Carbonates are an often-used record of seawater chemistry, but contaminants could bias the measured δ 60 Ni of bulk sediment. To isolate the true carbonate-bound δ 60 Ni signal, we optimized a chemical cleaning protocol designed to minimize non‑carbonate Ni contributions and maximize carbonate recovery. We analyzed ODP Site 1007 sediments and evaluated oxidative and reductive pre-cleaning steps and carbonate dissolution protocols. Our results show that only reductive cleaning significantly altered the subsequent carbonate leachate composition, lowering Ni/Ca ratios by up to 60% and δ 60 Ni values by as much as 0.4 ‰. In contrast, δ 60 Ni values were largely insensitive to premature carbonate dissolution during pre-cleaning or to partial leaching of silicates during carbonate dissolution, even at higher acid molarities or longer reaction times. We recommend an evidence-based protocol that removes hydro-soluble salts and clays, applies reductive cleaning and oxidative cleaning for certain sample compositions, and dissolves carbonate using 0.5 M acetic acid, adjusted to pH 5. Using these results, we infer a ∼ 0.9 ‰ Ni isotopic fractionation between chemically cleaned deep-water carbonates (+0.4 ± 0.1 ‰) and deep seawater. This method development is a key step toward accurately reconstructing ancient marine Ni cycles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

A Process Intensification Approach for CO 2 Absorption Using Amino Acid Solutions and a Guanidine Compound

Environmentally friendly amino-acid salt solutions are used for the absorption of carbon dioxide from concentrated flue-gas streams via chemical absorption. Process intensification reduces operating and capital costs by combining chemical reactions and separation operations. Here, we present a new process-intensification approach that combines the CO 2 capture and the amino-acid regeneration steps into a single process carried out in a slurry three-phase reactor. The absorbed CO 2 precipitates as a solid carbonated guanidine compound. The cycle is completed by separation of the solid precipitate to strip the CO 2 and regenerate the guanidine compound, while the liquid solution is recycled to the slurry reactor. The process was studied by modifying a model developed by the authors for a gas-liquid bubble column without the presence of the guanidine compound. The guanidine precipitation reaction was accounted for using kinetic parameters calculated by the authors in another study. The proposed model was implemented by modifying an existing computer code used for the simulation of gas-liquid bubble columns. The calculated results showed that the proposed cycle can significantly reduce energy, equipment, and operating costs and can make an important contribution to developing a competitive cost-effective large-scale process for CO 2 capture.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Reactive boride infusion stabilizes Ni-rich cathodes for lithium-ion batteries

Engineered polycrystalline electrodes are critical to the cycling stability and safety of lithium-ion batteries, yet it is challenging to construct high-quality coatings at both the primary- and secondary-particle levels. Here, we present a room-temperature synthesis route to achieve full surface coverage of secondary particles and facile infusion into grain boundaries, thus offering a complete “coating-plus-infusion” strategy. Cobalt boride metallic glass is successfully applied to Ni-rich layered cathode LiNi 0.8 Co 0.1 Mn 0.1 O 2 . Here, it dramatically improves the rate capability and cycling stability, including under high-discharge-rate and elevated-temperature conditions and in pouch full cells. The superior performance originates from simultaneous suppression of microstructural degradation of intergranular cracking and side reactions with electrolyte. Atomistic simulations identified the critical role of strong selective interfacial bonding, which offers not only a large chemical driving force to ensure uniform reactive wetting and facile infusion but also lowered the surface/interface oxygen activity, contributing to the exceptional mechanical and electrochemical stabilities of the infused electrode.

25 ENERGY STORAGE↗
DOE OSTI2020

Petaloid-shaped ZnO coated carbon felt as a controllable host to construct hierarchical Li composite anode

Prestoring Li metal into the 3D host via thermal infusion strategy has been considered as an effective approach on suppressing Li dendrites growth of Li-metal anode during cycling. However, the fast Li infusing process generally induces uncontrollable and undesirable structures during the formation of composite Li metal anode. It is widely accepted that both physical and chemical interactions between the molten Li and the hosts provide driving forces for Li infusing into the host, but which one plays the dominant role has not been explored clearly. In this work, a 3D carbon felt coated by petaloid zinc oxide (CFZO) is designed as a controllable host for prestoring Li metal via thermal infusion method. It is revealed that the morphology induced physical driving force plays a more important role than the chemical reaction between ZnO and molten Li in the thermal infusion process. The physical driving force originates from the capillarity effect, depending on the roughness of the host according to Wenzel's model. An adjustable Li infusing process can be controlled to fabricate the Li composite electrode with a hierarchical structure (with dense Li-rich layer and porous Li-poor layer). The unique structure of the CFZO-Li not only provides enough spaces for Li deposition, but also disperses local current density to induce a uniform Li deposition behavior, thus Li dendrites can be suppressed effectively. As a result, CFZO-Li anode exhibits promising cycle stability when coupled with both Li-containing (LiNi 0.8 Co 0.15 Al 0.05 O 2 ) and Li-free (sulfur) cathodes.

25 ENERGY STORAGE↗
DOE OSTI2025

Life cycle assessment of a novel gas switching reforming for sustainable hydrogen production with CO2 capture

Gas switching reforming for hydrogen production (GSR-H2) presents an efficient, low-carbon hydrogen production method that incorporates integrated carbon capture, offering efficiency gains over traditional methods such as proton exchange membrane (PEM) electrolysis, steam methane reforming (SMR) and the newer method of chemical looping reforming (CLR). GSR-H2 has been demonstrated in lab scale which operates as an exothermic process that eliminates the need for additional natural gas combustion, using its own waste heat to generate process steam and partially offset energy usage through electricity production. Beyond its thermal self-sufficiency, GSR-H2 advances upon CLR by integrating all reaction stages within a single reactor cluster, eliminating the complexities of solid circulation, reducing capital costs, and enhancing overall process efficiency. This streamlined design simplifies scale-up and enables inherent CO2 separation with minimal energy penalty, making GSR-H2 a highly competitive pathway for low-carbon hydrogen production. This study presents the first life cycle assessment (LCA) of GSR-H2, offering a novel evaluation of this new process’s environmental impacts across diverse energy scenarios. Key findings reveal that in the renewables-powered scenario, GSR-H2 achieves a GWP of 2.77 kg CO2 eq per kg H2, a substantial improvement over SMR’s 10.4 kg CO2 eq and close to the low emissions of CLR (1.84 kg CO2 eq) and PEM electrolysis (1.85 kg CO2 eq). These results demonstrate GSR-H2’s competitive advantage as a lower-emission alternative, combining design simplicity and efficiency gains, especially in renewable-integrated systems. These results establish GSR-H2 as a competitive, scalable option for hydrogen production, particularly in decarbonization efforts.

03 NATURAL GAS↗
DOE OSTI2021

Simultaneously Blocking Chemical Crosstalk and Internal Short Circuit via Gel-Stretching Derived Nanoporous Non-Shrinkage Separator for Safe Lithium-Ion Batteries

The separator, an ionic permeable and electronic insulating membrane between cathode and anode, plays a crucial role in the electrochemical and safety performance of batteries. However, the commercial polyolefin separators not only suffer from inevitable thermal shrinkage at elevated temperature, but also fail to inhibit the hidden chemical crosstalk of reactive gases such as O 2 , leading to often reported thermal runaway (TR) and hence preventing large-scale implementation of high-energy-density lithium-ion batteries. Herein, a nanoporous non-shrinkage separator (GS-PI) was fabricated via a novel gel-stretching orientation approach to eliminate TR. In situ synchrotron small angle X-ray scattering during heating clearly showed that the as-prepared thin GS-PI separator exhibits superior mechanical tolerance at high temperature, thus effectively preventing internal short circuit. Meanwhile, the unique nanoporous structure design further blocks chemical crosstalk and the associated exothermic reactions. Accelerating Rate Calorimetry test revealed that the practical 1 Ah LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NCM622)/graphite pouch cell using GS-PI nanoporous separator show a maximum temperature rise (dT/dt max ) of only 3.7 °C s -1 compared to 131.6 °C s -1 in the case of Al 2 O 3 @PE macroporous separator. Furthermore, despite the reduced pore size, the GS-PI separator demonstrates better cycling stability than conventional Al 2 O 3 @PE separator at high temperature without sacrificing specific capacity and rate capability.

25 ENERGY STORAGE↗
DOE OSTI2020

Probing the Effects of NO x and SO x Impurities on Oxy-Fuel Combustion in Supercritical CO 2 : Shock Tube Experiments and Chemical Kinetic Modeling

The direct-fired supercritical carbon dioxide cycles are one of the most promising power generation methods in terms of their efficiency and environmental friendliness. Two important challenges in implementing these cycles are the high pressure (300 bar) and high CO 2 dilution (>80%) in the combustor. The design and development of supercritical oxy-combustors for natural gas require accurate reaction kinetic models to predict the combustion outcomes. The presence of a small amount of impurities in natural gas and other feed streams to oxy-combustors makes these predictions even more complex. During oxy-combustion, trace amounts of nitrogen present in the oxidizer is converted to NO x and gets into the combustion chamber along with the recirculated CO 2 . Similarly, natural gas can contain a trace amount of ammonia and sulfurous impurities that get converted to NO x and SO x and get back into the combustion chamber with recirculated CO 2 . In this work, a reaction model is developed for predicting the effect of impurities such as NO x and SO x on supercritical methane combustion. The base mechanism used in this work is GRI Mech 3.0. H 2 S combustion chemistry is obtained from Bongartz et al. while NOx chemistry is from Konnov. The reaction model is then optimized for a pressure range of 30–300 bar using high-pressure shock tube data from the literature. It is then validated with data obtained from the literature for methane combustion, H 2 S oxidation, and NO x effects on ignition delay. The effect of impurities on CH 4 combustion up to 16 atm is validated using NO x -doped methane studies obtained from the literature. In order to validate the model for high-pressure conditions, experiments are conducted at the UCF shock tube facility using natural gas identical mixtures with N 2 O as an impurity at ~100 bar. Current results show that there is a significant change in ignition delay with the presence of impurities. A comparison is made with experimental data using the developed model and predictions are found to be in good agreement. The model developed was used to study the effect of impurities on CO formation from sCO 2 combustors. It was found that NO x helps in reducing CO formation while the presence of H 2 S results in the formation of more CO. The reaction mechanism developed herein can also be used as a base mechanism to develop reduced mechanisms for use in CFD simulations.

Energy & Fuels↗