Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “REDOX”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 1,585 records · Page 88
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Experimental demonstration of high-temperature (>1000 °C) heat extraction from a moving-bed oxidation reactor for thermochemical energy storage

Previously developed reduction-oxidation (redox) thermochemical energy storage technologies must store their products at high temperatures, complicating handling and transportation. This work describes a countercurrent, tubular, moving bed oxidation reactor at laboratory scale that produces high grade heat and allows solids to enter and exit the system at ambient temperatures. The particles implemented in the system consist of a novel magnesium manganese-oxide material well-suited for thermochemical energy storage. Output heat is obtained via a separate extraction gas flow, which exits from the middle portion of the main reactor tube. With this design, reactor temperatures in excess of 1000°C and extraction temperatures above 950°C were achieved. Deviation between the two measurements is a result of extraction thermocouple placement and losses in the reactor extraction arm; improvements to these parameters would bring the extraction temperature closer to the bed temperature. The reactor produces enough energy via oxidation to sustain both heat extraction and continued chemical reaction. During one representative steady state experiment at a particle flow rate of 1.5 g/s, an average of 447 W was extracted from the reactor out of an estimated 1083 W of released chemical energy for a duration of 70 minutes. Among the four experiments, the maximum bench-scale oxidation reactor energy efficiency of 36.2% and corresponding round-trip efficiency of 13.7% considering both redox reactors were demonstrated. Characteristics of an ideal system are considered and future improvements are proposed.

25 ENERGY STORAGE↗
DOE OSTI2025

A critical review of electrochemical heat pump technologies: Status, challenges, and perspectives

The development of advanced heat pump technologies is critical for reducing global energy consumption in the building sector, where space heating and cooling account for nearly 50% of energy use. Electrochemical heat pumps (EHPs) offer a promising alternative to vapor compression systems by enabling direct electrochemical-to-thermal energy conversion, often with environmentally benign working fluids that exhibit low or zero global warming potential (GWP). Prior literature has predominantly focused on chemically reactive heat pumps, while comprehensive assessments of electrochemical mechanisms remain limited. Here, this review addresses this gap by systematically evaluating the underlying principles, architectures, and performance metrics of EHP systems. Compared to conventional vapor compression systems, EHPs can achieve 10%-30% higher energy efficiency, with reported cooling coefficients of performance (COP c ) ranging from 3.5 to 14.3 under standard operating conditions. Despite these advantages, widespread adoption is hindered by challenges including membrane degradation, electrode fouling, sluggish redox kinetics, and elevated system-level capital costs. To address these limitations, the review outlines three research priorities: (i) the development of advanced membranes, catalysts, and electrode materials with enhanced chemical and mechanical stability; (ii) the application of molecular-level simulations for the rational design of high-performance redox-active working fluids; and (iii) the integration of advanced diagnostic techniques for real-time monitoring and sustained operation of EHPs. By consolidating recent advances and explicitly identifying technological and scientific gaps, this work uniquely contributes a comprehensive framework for guiding future electrochemical heat pump research and facilitating the transition to sustainable thermal management technologies.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2025

Manganese concentration influences nitrogen cycling in agricultural soil

Manganese (Mn) can modulate nitrogen (N) transformations in soil, yet its role in agroecosystems remains understudied. We conducted a 51-day microcosm incubation with agricultural soils differing in long-term N history (N 0 , no added N; N 1 , added 225 kg N ha −1 for a duration of 27 years) and amended with soluble Mn at 0 (M 0 ), 50 (M 1 ), or 250 (M 2 ) mg kg −1 and Glyceria striata (Lam.) residue. In N 1 soils, Mn additions (both M 1 and M 2 ) lowered total mineral N by 25 % relative to N 1 M 0 at day 51 and reduced 51-day cumulative N₂O by 32 % (N 1 M 1 ) and 42 % (N 1 M 2 ) vs. N 1 M 0 , whereas effects in N 0 were negligible. Mn also depressed ammonia-oxidizing bacterial amoA gene transcripts at day 15 in N 1 M 2 vs. N 1 M 0 (2.5 fold change). This reduction was likely due to increased N loss via complete denitrification to N₂ through microbial pathways such as nitrate/nitrite-dependent manganese oxidation (NDMO), where bacteria directly used the added Mn 2+ to reduce nitrate (NO 3 − ) and nitrite (NO 2 − ) to N 2 or as Mn dependent-ammonia oxidation (Mnammox) where bacteria oxidized ammonium (NH 4 + ) to N 2 , using Mn oxides as electron acceptors that formed from the oxidation of the added Mn. Other contributing mechanisms may include Mn-induced N immobilization, toxicity, and changes in the microbial community. These mechanistic results indicate that background Mn availability and redox dynamics can shape nitrification–denitrification pathways under N-rich conditions. In conclusion, we highlight how native Mn pools and redox state may help explain observed variability in N losses and greenhouse gas production across agricultural soils.

Decomposition↗
DOE OSTI2021

The role of thermodynamic features on the functional activity of electron bifurcating enzymes

Electron bifurcation is a biological mechanism to drive a thermodynamically unfavorable redox reaction through direct coupling with an exergonic reaction. This process allows microorganisms to generate high energy reducing equivalents in order to sustain life and is often found in anaerobic metabolism, where the energy economy of the cell is poor. Recent work has revealed details of the redox energy landscapes for a variety of electron bifurcating enzymes, greatly expanding the understanding of how energy is transformed by this unique mechanism. Here we highlight the plasticity of these emerging landscapes, what is known regarding their mechanistic underpinnings, and provide a context for interpreting their biochemical activity within the physiological framework. Here, we conclude with an outlook for propelling the field toward an integrative understanding of the impact of electron bifurcation.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Dry reforming of methane over Ni supported on LaMnO 3 thin films

Thin films of LaMnO 3 were deposited onto MgAl 2 O 4 by Atomic Layer Deposition (ALD) and studied as supports for Ni in the Dry Reforming of Methane (DRM). Scanning Transmission Electron Microscopy (STEM) with Energy-Dispersive X-ray Spectroscopy (EDS) demonstrated that LaMnO 3 covered the support uniformly, and X-ray diffraction (XRD) showed that the LaMnO 3 films maintained their perovskite structure after 5 redox cycles at 1073 K. The Ni also remained well dispersed after 5 redox cycles at 1073 K. The LaMnO 3 -supported catalyst was more active than Ni on the unmodified MgAl 2 O 4 and showed superior resistance against coke formation. Lastly, the results for Ni on the LaMnO 3 films are compared to previous results for Ni on LaFeO 3 , CaTiO 3 , SrTiO 3 , and BaTiO 3 films.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Sorbent-based oxygen separation with YBC114 for energy storage systems

In our report we aimed to design, build, and evaluate an oxygen separation system to provide an inert sweep gas with low oxygen partial pressure (pO2) to redox-active thermochemical energy conversion reactors for a range of applications, including two-step redox cycles for thermochemical energy storage, water splitting, and carbon-dioxide splitting. The separation is based on an oxygen-selective sorbent, YBaCo4O7+δ (YBC114), which has excellent oxygen sorption and desorption properties demonstrated in our previous work. The oxygen separation performance of YBC114 was comprehensively studied by thermogravimetric analysis, sorption breakthrough experiments, and temperature swing sorption - desorption cycles. The results reveal that YBC114 can produce inert sweep gas with an oxygen concentration of less than 100 ppmv for at least 20 min during the thermal swing adsorption (TSA) cycle with the current sorption bed configuration, and the performance is consistent from cycle to cycle. The optimal sorption and desorption temperatures for the TSA process with YBC114 are determined to be 300 °C and 500 °C, respectively. Although challenges remain for the current separation system (e.g., high sorption temperature and slow kinetics), this study demonstrates the potential to use the oxygen-selective sorbent to produce an inert sweep gas, the feasibility of the oxygen separation concept, and guides new sorbent material development to make this application economically practical. A simple procedure is described for designing the YBC114 oxygen separation process.

42 ENGINEERING↗
DOE OSTI2026

Temporal multi-omic analysis uncovers sex-biased molecular programs underlying skeletal muscle adaptation to endurance training

Background. Exercise training is known to benefit health and reduce disease risk. While adaptations in skeletal muscles are fundamental to many of the health benefits of exercise training, the common and sex-specific molecular regulators that mediate these adaptations remain to be fully elucidated. Methods. To this end, we leveraged skeletal muscle multi-omics data generated by the Molecular Transducers of Physical Activity Consortium (MoTrPAC), where 6 month-old male and female rats endurance trained for 1, 2, 4, or 8 weeks. Our objective was to identify shared and sex-specific multi-omic molecular responses to endurance training in skeletal muscle, and relate them to phenotypic adaptations. Results. We identified largely sexually-conserved transcriptomic and proteomic enrichments in the gastrocnemius, which correlated with skeletal muscle responses from a published exercise study in humans. We uncovered sex-consistent post-translational modifications, including decreased oxidation of MYH2 and deacetylation of the ß-oxidation enzyme HADHA. Pathway enrichment analyses revealed sex-specific remodeling across the acetylome, redox proteome, and phosphoproteome; females decreased mitochondrial protein oxidation and increased mitochondrial cristae proteins, indicative of enhanced redox buffering and mitochondrial efficiency. Despite observed decreases in the oxidation of key mitochondrial proteins, females displayed increases in the oxidation of proteins involved in glucose catabolism relative to males after 8 weeks of training, suggestive of sex-biased subcellular reactive oxygen species generation. Conclusions. This work shows a large portion of the adaptive response to endurance training in skeletal muscle is shared between females and males, while there are distinct and nuanced sex-specific adaptations that are evident, particularly at the level of post-translational regulation.

Many, Gina M.↗
DOE OSTI2025

Spatially resolved X-ray imaging and molecular characterisation of sulfur and iron in organic- and sulfur-rich hydrocarbon source mudstones

Sulfurisation of organic matter (OM) is a prominent preservation mechanism, however iron sulfide precipitation, particularly pyrite (FeS2), can counteract this mechanism. There is a dearth of high-resolution, spatially-resolved spectroscopic (redox) information on sulfur and iron inventories within organic-rich rocks that would improve our understanding of prevailing environmental conditions during deposition. Here, state-of-the-art synchrotron-based X-ray absorption and fluorescence analyses of key organic- and sulfur-rich mudstones demonstrate the potential of these techniques to non-destructively map and produce detailed spectroscopic information. Detailed high-resolution analyses (μm- to mm-scale) reveal the presence of widespread sulfurised OM in the Blackstone Band of the Kimmeridge Clay Formation, in line with a persistence of euxinia over a long temporal span and low reactive iron input, facilitating the preservation of OM through sulfurisation. In contrast, the presence of sulfurised OM was transitional in the Monterey Formation, consistent with fluctuating water column redox conditions, and is less significant in the Whitby Mudstone Formation, likely due to the high reactive iron concentrations outcompeting sulfurised OM formation. Analyses of sulfur species using model compounds further indicate that the Whitby Formation is strongly enriched in inorganic reduced sulfur minerals, while both the Kimmeridge Clay and Monterey Formations are dominated by organic sulfur species. These synchrotron-based observations improve our understanding of environmental conditions during the time of deposition of these mudstones and thus show great promise in the study of organic-rich sediments, especially in allowing their depositional settings to be more accurately reconstructed.

Kimmeridge Clay Formation↗
DOE OSTI2020

Shot noise sets the limit of quantification in electrochemical measurements

Detection of single molecules, particles, and rapid redox events is a challenge of electrochemical investigations and requires either an amplification strategy or significant averaging for the electrochemical current to exceed the noise level. We consider the minimum number of electrons required to reach the limit of quantification in these electrochemical measurements. A survey of the literature indicates that the state-of-the-art limit in current detection for different types of measurements (e.g. voltammetry, single-molecule redox cycling, ion channel recordings of single molecules, metal nanoparticle collision, and phase nucleation) is independent of the nature of the measurement and increases linearly with reciprocal response time, Δt -1 , over ~5 orders of magnitude (from ~10 to ~10 6 s -1 ). This paper demonstrates that the practical limit of quantification requires cumulative measurement of ~2100 electrons during Δt and is determined by statistics of counting electrons, that is, the shot noise in the current.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

An investigation on the impact of halidization on substituted dimethoxybenzenes

Functionalized organic molecules are emerging as charge storage materials in electrochemical technologies as the breadth and diversity of the organic design space offers the possibility of purpose-built materials with property sets optimized for a particular application. First developed as overcharge protection materials in lithium-ion batteries, substituted dialkoxybenzenes represent a potentially promising molecular platform for advancing soluble charge storage materials. In this study, we systematically substitute a series of halide groups at the 2- and 5-positions of the 1,4-dimethoxybenzene core, investigate the impact the halide groups have on molecular properties using electrochemical and spectroscopy methods, and compare these results to those of 2,5-dimethyl-1,4-dimethoxybenzene (25DDB), a previously reported derivative. In general, we observe that introduction of heavy halogen atoms leads to decreased gravimetric capacity as compared to 25DDB, but concomitantly improves solubility and redox potentials. As the halide functional group increases in size, the active material becomes less stable in its oxidized state as evinced by both cyclic voltammetry and bulk electrolysis cycling. None of the halogenated species are as stable as 25DDB indicating that these materials may be better suited for applications with more rapid cycling conditions (e.g., redox shuttling). More broadly, these results may serve as a useful data set for computational methods for materials discovery and optimization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Self-supported MoO 2 /MoS 2 nano-sheets embedded in a carbon cloth as a binder-free substrate for high-energy lithium–sulfur batteries

As one of the most prospective candidates for next-generation rechargeable batteries, lithium-sulfur (Li-S) batteries currently still encounter great challenges associated with the low conductivity, severe shuttle effects, and sluggish redox kinetics. Herein, a self-supported sulfur host is fabricated by an in-situ growth of MoO 2 /MoS 2 nano-sheets on a carbon cloth (CC). First, carbon cloth serves as a good template for the morphology-controlled synthesis of nanostructured materials, which not only alleviates the agglomeration of MoO2/MoS2, but also enhances the flexibility and mechanical strengthen of the hybrid architecture as a free-standing host. Second, the polysulfide-trapping ability can be greatly enhanced by both physical and chemical adsorption from the MoO 2 /MoS 2 -anchored carbon cloth. Moreover, the partially sulfurized MoO 2 /MoS 2 nano-sheets integrate the benefits of conductive MoO 2 and sulfiphilic MoS 2 , thus facilitating fast charge transfer and redox kinetics of polysulfide conversion. As a result, these attributes enable the host to hold a high sulfur loading (up to 7.6 mg cm -2 ), which exceeds most of the reported carbon cloth-related cathode work in the literature. Furthermore, the Li-S cells can achieve a high peak capacity of 1350 mA h g -1 , excellent rate capability (C/20 - 2C rate), impressive areal capacity (up to 6.3 mA h cm -2 ), and a high capacity retention of 85% after 100 cycles.

25 ENERGY STORAGE↗
DOE OSTI2023

Geometrical and chemical effects on the electrochemistry of single-wall carbon nanotube (SWCNT) network electrodes

Single-wall carbon nanotube (SWCNT) network is a promising electrode material for bio detection. Unfortunately, the associations between their physical as well as chemical properties and observed electrochemical performance are not known. This hinders any systematic optimization of the network properties towards specific analytes. Here we present a consistent physicochemical and electrochemical characterization of differently treated SWCNT networks. The results unambiguously show that (i) even if the electrochemical properties of different electrodes are practically identical when assessed by surface insensitive outer sphere redox (OSR) probes their behavior with inner sphere redox (ISR) probes can be drastically different. Further, (ii) the choice of the modification method (structural, chemical, electrochemical) heavily depends on nature of the target analyte, which are typically ISR probes. Although, (iii) chemical changes in the carbon phase appeared to be minor, effects of different treatments on oxidation states of Fe appeared to have a strong effect on the electrochemical performance of the networks in the case of ISR probes.

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

Mitigation of polysulfide shuttle effect in Li-S batteries through catalytic disproportionation reaction

Polysulfides are poorly retained within porous cathodes and readily diffuse into the electrolyte over time, leading to the well-known shuttle effect that undermines the reversibility of Li-S batteries. Here, in this study, we demonstrate that catalytic disproportionation of polysulfides provides an effective pathway to suppress this process by rapidly converting dissolved species into solid sulfur and sulfides, thereby preventing their migration into the electrolyte. Fundamentally, the sluggish kinetics of sulfur redox reactions are responsible for the accumulation and redistribution of soluble polysulfides in the bulk electrolyte. By accelerating these kinetics, catalyzed disproportionation not only confines sulfur within the conductive cathode matrix but also promotes the homogeneous precipitation of Li₂S₂/Li₂S, which enhances electrochemical reversibility and cycling stability. Using nitrogen-doped carbon (NC800) as a model catalyst, we reveal its ability to drive a pseudo-16-electron reduction pathway, leading to a single dominant Li₂S product and uniform deposition within the porous framework. In contrast, a non-catalytic carbon (KB) yields multiple polysulfide intermediates and heterogeneous deposition. The mechanistic insights provided here highlight the pivotal role of catalytic disproportionation in reshaping sulfur redox pathways and offer a rational strategy for mitigating polysulfide shuttling in practical Li-S pouch cells.

25 ENERGY STORAGE↗
DOE OSTI2020

Unraveling Na and F coupling effects in stabilizing Li, Mn-rich layered oxide cathodes via local ordering modification

Regardless of the prevailing capacity and energy density of lithium, manganese-rich layered oxide (LMR-NMC) cathodes, continuous decay of voltage and overall energy density during cycling hinders this material from commercialization in Li-ion batteries. Although significant work focuses on single doping of Na and F, analysis in portraying the benefit of these ions in diminishing the structural distortion during activation cycle is in doubt. In this study, the effects of co-doping Na and F into the LMR-NMC structure in stabilizing the structure and mitigating oxygen loss during the first cycle are closely examined via in situ x-ray measurements. Na and F co-doping shows a 30% lower degree of Li + /Ni 2+ mixing in the Li layer (C2/m structure), 50% reduced Debye-Waller factor of Mn-O bonding, increase reversible TM migration, and faster Li diffusion relative to the pristine material. Due to the utilization of Ni redox chemistry below 4.4 V, less oxygen redox is required for charge compensation at high voltage. This study offers the first instance to quantitatively evaluate the effects of co-doping Na and F in LMR-NMC cathode in order to minimize voltage degradation by altering the local ordering of O3-type structure, which may rationalize strategies to overcome the issues of the material.

25 ENERGY STORAGE↗
DOE OSTI2021

A high-performance organic cathode customized for sulfide-based all-solid-state batteries

All-solid-state batteries (ASSBs) have become increasingly attractive recently due to their better safety and prospective long-term stability compared with conventional liquid batteries. However, obtaining a sustainable cathode candidate to match the solid electrolyte with regards to operating potential, chemical compatibility, and mechanical property is still an open challenge. In this work, the chemical incompatibility of quinone-based active materials and sulfide-based electrolyte were unveiled for the first time through a heteroconjugate addition reaction mechanism. To develop a quinone cathode customized for sulfide-based ASSBs, poly-(anthraquinonyl sulfide)-graphene (PAQS-G) nanocomposite was reported. The stable polymer framework of PAQS can protect the quinone redox center by preventing nucleophilic attack from sulfide-based solid electrolytes. The graphene additives can ameliorate redox kinetics and improve active material utilization. The PAQS-G cathode exhibited a specific capacity of ~178 mAh g -1 and a high material utilization of ~79%. Excellent cycling stability was achieved with 94 % capacity after 200 cycles in lithium batteries and 95.5 % capacity after 300 cycles in sodium batteries at 0.1C rate, respectively. A promising potential for energy storage applications was demonstrated.

25 ENERGY STORAGE↗
DOE OSTI2021

Influence of trace level As or Ni on pyrite formation kinetics at low temperature

Pyrite formation at low temperature during early diagenesis in (sub-)surface sediments is an essential step of Fe and S biogeochemical cycles and the presence of this ubiquitous mineral of surface environments is often used as an indicator of paleo-redox conditions. Pathways of pyrite formation are usually discussed in environmental settings by involving a variety of nanosized Fe-S mineralogical precursors as a function of the local geochemical conditions. However, the influence of trace element impurities such as Ni and As in the solution at the time of pyrite formation has been poorly studied, whereas specific chemical signatures of trace elements are commonly observed in sedimentary pyrites. Here, a better understanding of the impact of Ni and As incorporation at trace levels on pyrite formation is essential to help refining the use of these elements as paleo-redox indicators and to evaluate the role of pyrite as a sink regulating the biogeochemical cycle of potentially toxic trace elements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Simulation of anoxic lenses as exporters of reactivity in alluvial aquifer sediments

Sedimentary interfaces between contrasting hydrogeological facies in alluvial aquifers drive the development of biogeochemical interfaces that influence subsurface and surface water quality. Here, we calibrate a reactive transport model on a series of dual-domain column experiments, where centimeter-scale, low-permeability, organic-rich anoxic lenses are embedded in coarser-grained aquifer material. Simulations explicitly account for C, Fe, and S cycling at the interface between the lenses and the aquifer in water-saturated conditions. Our results highlight the role of fine-grained, organic-rich inclusions not only as sources or sinks for redox-sensitive species, but also as exporters of nutrients that stimulate downgradient biogeochemical cycling. By releasing large amounts of organic carbon into the surrounding aquifer, such lenses drive the development of proximal secondary reduction zones ("halos"), characterized by high microbial activity (e.g., sulfate reduction) and accumulation of reduced reaction products (e.g., iron sulfide). If similar secondary reduction zones develop within the hydraulically conductive domain of an aquifer, they would be highly susceptible to changes in hydrologic conditions, for instance oxygen pulses associated with seasonal snowmelt. Furthermore, our results also emphasize the limitations of relying solely on aqueous species measurements to inform reactivity in systems where fast redox cycling and/or sizeable particulate transport may limit the signature of reactivity in the dissolved phase.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Lytic polysaccharide monooxygenase synergized with lignin-degrading enzymes for efficient lignin degradation

Even though the discovery of lytic polysaccharide monooxygenases (LPMOs) has fundamentally shifted our understanding of biomass degradation, most of the current studies focused on their roles in carbohydrate oxidation. However, no study demonstrated if LPMO could directly participate to the process of lignin degradation in lignin-degrading microbes. This study showed that LPMO could synergize with lignin-degrading enzymes for efficient lignin degradation in white-rot fungi. The transcriptomics analysis of fungi Irpex lacteus and Dichomitus squalens during their lignocellulosic biomass degradation processes surprisingly highlighted that LPMOs co-regulated with lignin-degrading enzymes, indicating their more versatile roles in the redox network. Biochemical analysis further confirmed that the purified LPMO from I. lacteus CD2 could use diverse electron donors to produce H 2 O 2 , drive Fenton reaction, and synergize with manganese peroxidase for lignin oxidation. The results thus indicated that LPMO might uniquely leverage the redox network toward dynamic and efficient degradation of different cell wall components.

59 BASIC BIOLOGICAL SCIENCES↗