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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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At least 361 records · Page 20
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

A Synoptic VLBI Technique for Localizing Nonrepeating Fast Radio Bursts with CHIME/FRB

We demonstrate the blind interferometric detection and localization of two fast radio bursts (FRBs) with subarcminute precision on the 400 m baseline between the Canadian Hydrogen Intensity Mapping Experiment (CHIME) and the CHIME Pathfinder. In the same spirit as Very Long Baseline Interferometry (VLBI), the telescopes were synchronized to separate clocks, and the channelized voltage (herein referred to as baseband) data were saved to a disk with correlation performed offline. The simultaneous wide field of view and high sensitivity required for blind FRB searches implies a high data rate—6.5 terabits per second (Tb/s) for CHIME and 0.8 Tb s{sup −1} for the Pathfinder. Since such high data rates cannot be continuously saved, we buffer data from both telescopes locally in memory for ≈40 s, and write to the disk upon receipt of a low-latency trigger from the CHIME Fast Radio Burst Instrument (CHIME/FRB). The ≈200 deg{sup 2} field of view of the two telescopes allows us to use in-field calibrators to synchronize the two telescopes without needing either separate calibrator observations or an atomic timing standard. In addition to our FRB observations, we analyze bright single pulses from the pulsars B0329+54 and B0355+54 to characterize systematic localization errors. Our results demonstrate the successful implementation of key software, triggering, and calibration challenges for CHIME/FRB Outriggers: cylindrical VLBI outrigger telescopes which, along with the CHIME telescope, will localize thousands of single FRB events with sufficient precision to unambiguously associate a host galaxy with each burst.

47 OTHER INSTRUMENTATION↗
DOE OSTI2022

Electrostatic Asymmetry of Wurtzite Nanocrystals and Resulting Photocatalytic Properties

Efficient light absorption and high energy of charge carriers of zinc cadmium sulfide (ZCS) make this semiconductor attractive for many photocatalytic reactions. Despite marked successes in shape-controlled synthesis of ZCS central to their photocatalytic performance, recombination of charge carriers as they migrate through the nanoscale particles results in losses of excitation energy, markedly reducing the photocatalytic activity of ZCS and other heterogeneous photocatalysts. Here, in this study, we show that the electrostatic asymmetry of nanostructures, previously discovered for nearly spherical nanoparticles, also manifests in wurtzite ZCS with planar geometry. The electrostatic asymmetry assists charge separation and substantially increases the yield of photocatalytic reactions in monocrystalline ZCS. The synthesized ZCS nanorods and nanoplates with identical chemical composition were found to have markedly different photocatalytic activity for evolution of hydrogen in water. Despite much smaller specific surface areas, the ~500 nm wide nanoplates displayed a hydrogen evolution rate 12 times higher than the ~35 nm long nanorods, also outperforming other ZCS photocatalysts. Experimental and computational data indicate that the homo- and heterojunction-free ZCS nanoplates with continuous wurtzite lattice behave essentially as nanoscale dipoles with intrinsic dipole moment as high as 48.39 D per unit cell. Electric-field-directed migration of charge carriers stimulates their localization on opposite parts of the nanoplates. Direct imaging of the intraparticle electrical field using off-axis electron holography confirmed their electrostatic asymmetry. Polarization-enhanced charge separation provides a new pathway to efficient and stable photocatalysts for sustainable energy technologies.

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

Reduced Order Models for Liquid Hydrogen Pooling and Vaporization Supported by Experiments

In the event of a leak of liquid hydrogen, a pool can form that vaporizes, disperses, and eventually dilutes to a non-flammable mixture. In this work, we describe fast-running models for the pooling and vaporization of liquid hydrogen in a steady cross-wind. Several pooling models from the literature are compared to solve for the flow and extent of the pool. The size of the pool can serve as the source for a separate dispersion model, which builds upon the existing one-dimensional Gaussian plume model in HyRAM+. Additional terms for the effects of a cross-wind on momentum and entrainment were added so that the model could handle the effects of a cross-wind on a low-speed flow. The models are compared to experimental data on pooling extent and downwind dispersion for steady flow rates of liquid hydrogen in a steady cross-wind. In the two compared experiments, liquid flow rates of 15 and 45 g/s were spilled onto concrete in cross-winds of approximately 1.8 m/s. The rate of growth of the pool and the downwind concentration boundaries are compared to the models, showing good agreement, although additional tuning is needed. These models can contribute to the advancement of codes and standards for liquid hydrogen systems.

dispersion↗
DOE OSTI2024

A sustainable cobalt separation with validation by techno-economic analysis and life-cycle assessment

Sustainable, cost-effective cobalt/nickel separations chemistry contributes to the realization of economically competitive lithium-ion battery recycling, as well as primary mining of cobalt and nickel. Such improvements can address supply chain challenges for cobalt, a critical element. Herein, we disclose a simple method for separating Co/Ni by second coordination-sphere molecular recognition. Selective cobalt precipitation is achieved using carbonate ions in an ammonia solution due to the outer-sphere, hydrogen bonding interactions between [Co(NH 3 ) 6 ] 3+ and CO 3 2− , evaluated with density functional theory calculations. We demonstrate this method on mixtures of Co/Ni chlorides comprising a 10-fold excess of Ni and provide comparisons with ore-processing systems. High purities (99.4(3)% Co; 98.2(4)% Ni) and recoveries (77(8)% Co; ∼100% Ni) were observed for both Co- and Ni-enriched products using optimized conditions. In conclusion, this method is potentially economically competitive based on initial techno-economic analysis (TEA) and life-cycle assessment (LCA) that also illustrate advantages in terms of sustainability.

cobalt↗
DOE OSTI2023

Multi-functionalized basic immobilized amine sorbents for removal of metal contaminants from wastewater

This disclosure provides polyamine sorbent compositions for the separation of metals from aqueous solutions. The polyamine sorbent compositions comprise a silica support, an aminosilane bound to the silica support, an epoxysilane bound to the silica support, and a polyamine where the polyamine is chemically tethered onto a solid silica support through via the epoxysilane. The polyamine may be further stabilized within the bulk sorbent through hydrogen bonding interactions with the aminosilane. The sorbent compositions resist leaching by H 2 O in an aqueous stream containing heavy oxyanion-based (and other) metals and demonstrate stability over a pH range of 2-14. The sorbent compositions are useful for the separation of metals from aqueous solutions. The cationic heavy metals are captured by the co-existing amine groups (—NH 2 , —NH, —N) from the polymeric network while additional metal capture capacity is derived from the introduction of a secondary silane linker.

Gray, McMahan L.↗
DOE OSTI2022

Decomposition of PVDF to delaminate cathode materials from end-of-life lithium-ion battery cathodes

The growing demand of electric vehicles and rapid consumption of rechargeable lithium-ion batteries (LIBs) require recycling of spent cathode active materials (CAMs) to reduce hazardous wastes and supply raw materials to LIB production. To separate CAMs from the cathode, direct calcination of polyvinylidene fluoride (PVDF) binder is widely applied, which leads to high energy consumption and release of toxic hydrogen fluoride. It is desirable to have an environmentally friendly and effective alternative to traditional direct calcination. In this study, five lithium salts, LiOAc (lithium acetate), LiNO 3 , LiCl, Li 2 CO 3 , and Li 2 SO 4 , were deployed and compared for their performance in recycling CAMs. A peel-off efficiency of up to 98.5% was achieved at a LiOAc to LiNO 3 molar ratio of 3:2, salt to cathode mass ratio of 10:1, and temperature of 300 °C at a holding time of 30 min. This system avoids corrosive chemicals and minimizes particle agglomeration of recycled products. Compared with sodium salt systems (NaOAc-NaNO 3 ) or direct calcination, the LiOAc-LiNO 3 system prevented high reaction temperature or further lithium loss and minimized crystal structure and morphological changes. In conclusion, a decomposition mechanism of PVDF through adsorption of HF and fluorine substitution was proposed.

25 ENERGY STORAGE↗
DOE OSTI2021

Photodepositing CdS on the Active Cyano Groups Decorated g‐C 3 N 4 in Z‐Scheme Manner Promotes Visible‐Light‐Driven Hydrogen Evolution

Abstract g‐C 3 N 4 /CdS heterojunctions are potential photocatalysts for hydrogen production but their traditional type‐II configuration generally leads to weak oxidative and reductive activity. How to construct the novel Z‐scheme g‐C 3 N 4 /CdS counterparts to address this issue remains a great challenge in this field. In this work, a new direct Z‐scheme heterojunction of defective g‐C 3 N 4 /CdS is designed by introducing cyano groups (NC‐) as the active bridge sites. Experimental observations in combination with density functional theory (DFT) calculations reveal that the unique electron‐withdrawing feature of cyano groups in the defective g‐C 3 N 4 /CdS heterostructure can endow this photocatalyst with numerous advantageous properties including high light absorption ability, strong redox performance, satisfactory charge separation efficiency, and long lifetime of charge carriers. Consequently, the resultant photocatalytic system exhibits more active performance than CdS and g‐C 3 N 4 under visible light and reaches an excellent hydrogen evolution rate of 1809.07 µmol h −1 g −1 , which is 6.09 times higher than pristine g‐C 3 N 4 . Moreover, the defective g‐C 3 N 4 /CdS photocatalyst maintains good stability after 40 h continuous test. This work provides new insights into design and construction of Z‐scheme heterojunctions for regulating the visible‐light‐induced photocatalytic activity for H 2 evolution.

Wang, Zhipeng↗
DOE OSTI2021

Site‐Specific Reduction‐Induced Hydrogenation of a Helical Bilayer Nanographene with K and Rb Metals: Electron Multiaddition and Selective Rb + Complexation

Abstract The chemical reduction of π‐conjugated bilayer nanographene 1 (C 138 H 120 ) with K and Rb in the presence of 18‐crown‐6 affords [K + (18‐crown‐6)(THF) 2 ][{K + (18‐crown‐6)} 2 (THF) 0.5 ][C 138 H 122 3− ] ( 2 ) and [Rb + (18‐crown‐6) 2 ][{Rb + (18‐crown‐6)} 2 (C 138 H 122 3− )] ( 3 ). Whereas K + cations are fully solvent‐separated from the trianionic core thus affording a “naked” 1 .3 − anion, Rb + cations are coordinated to the negatively charged layers of 1 .3 − . According to DFT calculations, the localization of the first two electrons in the helicene moiety leads to an unprecedented site‐specific hydrogenation process at the carbon atoms located on the edge of the helicene backbone. This uncommon reduction‐induced site‐specific hydrogenation provokes dramatic changes in the (electronic) structure of 1 as the helicene backbone becomes more compressed and twisted upon chemical reduction, which results in a clear slippage of the bilayers.

Zhou, Zheng↗
DOE OSTI2021

Site‐Specific Reduction‐Induced Hydrogenation of a Helical Bilayer Nanographene with K and Rb Metals: Electron Multiaddition and Selective Rb + Complexation

Abstract The chemical reduction of π‐conjugated bilayer nanographene 1 (C 138 H 120 ) with K and Rb in the presence of 18‐crown‐6 affords [K + (18‐crown‐6)(THF) 2 ][{K + (18‐crown‐6)} 2 (THF) 0.5 ][C 138 H 122 3− ] ( 2 ) and [Rb + (18‐crown‐6) 2 ][{Rb + (18‐crown‐6)} 2 (C 138 H 122 3− )] ( 3 ). Whereas K + cations are fully solvent‐separated from the trianionic core thus affording a “naked” 1 .3 − anion, Rb + cations are coordinated to the negatively charged layers of 1 .3 − . According to DFT calculations, the localization of the first two electrons in the helicene moiety leads to an unprecedented site‐specific hydrogenation process at the carbon atoms located on the edge of the helicene backbone. This uncommon reduction‐induced site‐specific hydrogenation provokes dramatic changes in the (electronic) structure of 1 as the helicene backbone becomes more compressed and twisted upon chemical reduction, which results in a clear slippage of the bilayers.

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

Unraveling Hydrogen Induced Geochemical Reaction Mechanisms through Coupled Geochemical Modeling and Machine Learning

Underground hydrogen storage (UHS) provides a promising large-scale, long-term energy storage solution. A reasonable recovery of stored hydrogen is critical for a successful storage scheme. However, in subsurface reservoirs hydrogen is subject to active geochemical reactions that might result in hydrogen loss. In this study, we implemented a geochemical modeling approach coupled with an unsupervised machine learning technique called non-negative matrix factorization (NMF) to unravel the complex brine-rock-H 2 geochemical processes responsible for hydrogen losses, with particular focus on sulfate reduction reactions. NMF is applied to modeled mineral evolution and fluid component profiles to retrieve profiles that can be interpreted to more easily assess competing processes. NMF decouples simulated competing equilibrium reactions. This facilitates separation of overlapping reaction profiles from redox processes, dissolution fronts, and secondary precipitation while considering the effects of simulation parameters such as salinity, temperature, and total H 2 pressure. NMF successfully discriminates these competing effects in nonlinear ways, allowing robust interpretation. In addition, NMF reveals subtle coupled mineral associations and reaction fronts that are invisible to conventional model analysis. This integrated approach strengthens the conceptual understanding of complex nonlinear hydrogen-brine-rock interactions and advances geochemical research on UHS systems to resolve complexities in modeled geochemical systems without the need for direct experiments or prior knowledge. Furthermore, this study highlights the efficacy of combining geochemical modeling with machine learning techniques to enhance the interpretability of the intricate geochemical simulation output through deciphering the overlapping reaction path that cannot be achieved only using conventional analysis of geochemical models alone.

08 HYDROGEN↗
DOE OSTI2023

What do far-infrared spectra of solitary water in “water-in-solvent” systems reveal about water’s solvation and dynamics?

Classical molecular dynamics simulations of water in ionic and dipolar solvents were used to interpret the far-infrared (FIR) rotation/libration spectra of “solitary water” in terms of water’s rotational dynamics and interactions with solvents. Seven solvents represented by nonpolarizable all-atom force fields and a series of idealized variable-charge solvents were used to span the range of solvent polarities (hydrogen bonding) studied experimentally. Simulated spectra capture the solvent dependence observed, as well as the relationship between the frequencies of water libration (νL) and OH stretching bands (νOH). In more strongly interacting solvents, simulated νL are ∼20% higher than those of experiment. In all solvents, the simulated spectra are composites of rotational motions about the two axes perpendicular to water’s dipole moment, and the different frequencies of these two motions are responsible for the breadth of the libration band and the bimodal shape observed in halide ionic liquids. Simulations overestimate the separation of these two components in most solvents. The character of water rotational motions changes markedly with solvent polarity, from quasi-free rotation in nonpolar and weakly polar solvents to highly constrained libration in strongly hydrogen bonding environments. The changeover to librational motions dominating the spectrum occurs between solvents such as benzene (νL ∼ 250 cm−1) and acetonitrile (νL ∼ 400 cm−1). For solvents in the latter category, the mean frequency of the experimental FIR band provides a direct measure of mean-squared torques and, therefore, force constants associated with interactions constraining water’s librational motion.

Chemistry↗
DOE OSTI2020

Savannah River Site High Level Radioactive Waste Tank Sample Thermolytic Hydrogen Generation - 20346

To support the revision of flammability calculations and controls for the Savannah River Site (SRS) High-Level Radioactive Waste (HLW) tanks, Savannah River National Laboratory (SRNL) conducted laboratory measurements with the goal of quantifying hydrogen produced in HLW by non-radiolytic chemical reactions (i.e., thermolysis). Testing was performed with HLW tank supernate samples that represented a cross section of types of waste at SRS, including tanks that store typical evaporator concentrate, dissolved salt-cake, dilute recycle stream from the Defense Waste Processing Facility (DWPF), evaporator concentrate of the recycle stream from DWPF, fresh waste from the canyon separations facility, and waste that has been through salt processing cesium removal. Non-radioactive simulant testing included the classes of organic compounds historically introduced into the HLW tanks that were recently shown to be the most active toward the thermolytic generation of hydrogen. The reaction rate equations developed for thermolytic hydrogen generation from each class of organic compound showed direct proportionality to organic compound concentration and hydroxide concentration. Simulant testing identified that highly concentrated waste with high hydroxide concentration had the highest rates of thermolytic hydrogen generation. Using the radioactive tank sample thermolysis measurements at high temperatures and the mechanistic salt dependence of the simulant models, a global model was developed for tank waste thermolytic hydrogen generation as a function of total organic carbon content of SRS HLW. Through the primary functionality of the global model (organic carbon and free hydroxide concentration), the relative reactivity of the organic carbon in the waste was quantified. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2025

Exploring Microphase Separation in Semi-Fluorinated Diblock Copolymers: A Combined Experimental and Modeling Investigation

We report the combined experimental and theoretical study of the bulk self-assembly behavior of polystyrene-blockpoly( 2,3,4,5,6-pentafluorostyrene) diblock copolymers. These block copolymers were designed to create highly antagonistic blocks (with a high Flory−Huggins interaction parameter, χ) with minimum disruption to the molecular construct (i.e., only replacing five hydrogen atoms with five fluorine atoms). A large library of diblock copolymers (41 samples) was synthesized by reversible addition− fragmentation chain transfer (RAFT) polymerization to map out a major portion of the phase space. All block copolymers exhibited narrow molecular weight distributions with dispersity (D) values between 1.07 and 1.32, and subsequent thermal annealing revealed phase separation into well-defined nanoscale morphologies depending on their molecular composition, as determined from small-angle X-ray scattering and transmission electron microscopy analyses, with an experimental phase diagram being constructed. The χ value at 25 °C for this block copolymer was estimated to be 0.2 using strong segregation theory, based on trends in phase-separated domain spacing and interfacial width. When applying theoretical approaches, the majority of the domain spacing data trends were captured by a coil−coil diblock copolymer model; however, a better fit to the data for samples with shorter fluorinated blocks was obtained with a rod−coil model, indicating that the chains in these fluorinated blocks likely have a higher inherent stiffness and were thus rod-like. This observation demonstrates that, due to the very high value of χ, a transition from coil−coil to rod−coil behavior can be obtained purely by reducing the length of the stiffer of the two blocks and without varying temperature or the chemical composition of the polymers. Here, this work showcases the presence of strong microphase separation within AB diblock copolymers despite the relatively similar chemical composition of the constituent “A” and “B” units, with a clear transition from rod−coil to coil−coil segregation behavior.

RAFT polymerization↗
DOE OSTI2021

Current status of biogas upgrading for direct biomethane use: A review

Anaerobic digestion produces biogas, a mixture of CH 4 and CO 2 , where CH 4 is a low cost, environmentally friendly, and renewable energy source. The application of biogas production is increasing rapidly as a means of reducing the pollution impact of organic biomasses. However, biogas contains unwanted elements such as hydrogen sulfide, carbon monoxide, siloxanes, and carbon dioxide. To remove these elements, several biogas upgrading technologies like water scrubbing, amine scrubbing, pressure swing adsorption, and membrane separation have been developed and are being used at various commercial scales. Problems with these methods are high energy consumption, the use of expensive chemicals, and high operating cost. Therefore, a major effort is currently underway to improve the design of existing methods as well as developing innovative new upgrading technologies such as cryogenic separation and biological upgrading. Here, this review intends to provide a comprehensive overview of the limitations with the existing upgrading technologies along with recent advances in physical, chemical, and biological biogas upgrading technologies (e.g., pressure swing adsorption, membrane separation, biochar adsorption and CO 2 conversion by biological organisms) and further into possible future solutions, such as hybrid systems. Comparative studies of process complexities and associated economic concerns are also provided, and future perspectives that may facilitate research into sustainable biogas upgrading technologies are discussed, focusing in particular on cryogenic separation, novel biological techniques, biochar based upgrading and hybrid technologies incorporating two or more different methods seamlessly integrated.

09 BIOMASS FUELS↗
DOE OSTI2022

Trumpler 16-26: a new centrifugal magnetosphere star discovered via SDSS/APOGEE H -band spectroscopy

ABSTRACT We report the discovery of a new example of the rare class of highly magnetized, rapidly rotating, helium enhanced, early B stars that produce anomalously wide hydrogen emission due to a centrifugal magnetosphere (CM). The star is Trumpler 16-26, a B1.5 V member of the Trumpler 16 open cluster. A CM was initially suspected based on hydrogen Brackett series emission observed in SDSS/APOGEE H-band spectra. Similar to the other stars of this type, the emission was highly variable and at all times remarkable due to the extreme velocity separations of the double peaks (up to 1300 km s−1.) Another clue lay in the TESS light curve, which shows two irregular eclipses per cycle when phased with the likely 0.971 8115-d rotation period, similar to the behaviour of the well-known CM host star σ Ori E. To confirm a strong magnetic field and rotation-phase-locked variability, we initiated a follow-up campaign consisting of optical spectropolarimetry and spectroscopy. The associated data revealed a longitudinal magnetic field varying between −3.1 and +1.6 kG with the period found from photometry. The optical spectra confirmed rapid rotation (v sin i = 195 km s−1), surface helium enhancement, and wide, variable hydrogen emission. Tr16-26 is thus confirmed as the 20th known, the fourth most rapidly rotating, and the faintest CM host star yet discovered. With a projected dipole magnetic field strength of Bd > 11 kG, Tr16-26 is also among the most magnetic CM stars.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2021

Impact of Water Extraction on Malonamide Aggregation: A Molecular Dynamics and Graph Theoretic Approach

Solution structure in liquid-liquid extraction affects the efficacy of separation; however, even for simplified organic phases, structural characterization and attribution of aggregation to intermolecular interactions are fundamental challenges. We investigate water uptake into organic phases for two malonamides commonly applied to actinide and lanthanide separations. Extracted water induces reorganization of the amphiphilic extractant molecules, although we find this rearrangement is not strongly manifested in small-angle X-ray scattering making it challenging to probe without methods such as atomistic simulation. Using a graph theoretic approach to define hydrogen bonded water/malonamide aggregates from molecular dynamics simulations, we find evidence of a characteristic aggregate size by water number that results from geometric accommodation of the surrounding malonamide molecules. Furthermore, this implies a degree of size selectivity inherent to these water-in-oil aggregates. Conversely, we find no evidence of a characteristic size of the aggregates with respect to their malonamide number. By defining a separate graphical representation of self-association of the amphiphilic malonamides, we quantify how water affects the local and nonlocal topology of the malonamide network, providing a basis for characterization of the structure and impact of polar solutes in increasingly complex organic phases.

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

Influences of Hydrogen Bonding-Based Stabilization of Bolaamphiphile Layers on Molecular Diffusion within Organic Nanotubes Having Inner Carboxyl Groups

This paper reports molecular diffusion behavior in two bolaamphiphile-based organic nanotubes having inner carboxyl groups with different inner dimeters (10 and 20 nm) and wall structures, COOH-ONT 10nm and COOH-ONT 20nm , using imaging fluorescence correlation spectroscopy (imaging FCS). Here, the results were compared to those previously obtained in a similar nanotube with inner amine groups (NH 2 -ONT 10nm ). COOH-ONT 10nm , as with NH 2 -ONT 10nm , were formed from a rolled bolaamphiphile layer incorporating triglycine moieties, whereas COOH-ONT 20nm consisted of four stacks of triglycine-free bolaamphiphile layers. Imaging FCS measurements were carried out for anionic sulforhodamine B (SRB), zwitterionic/cationic rhodamine B (RB) and cationic rhodamine-123 (R123) diffusing within ONTs (1–9 µm long) at different pH (3.4–8.4) and ionic strengths (1.6–500 mM). Diffusion coefficients (D) of these dyes in the ONTs were very small (0.01–0.1 µm 2 /s), reflecting the significant contributions of molecule-nanotube interactions to diffusion. The D of SRB was larger at higher pH and ionic strength, indicating the essential role of electrostatic repulsion that was enhanced by the deprotonation of the inner carboxyl groups. Importantly, the D of SRB was virtually independent of nanotube inner diameter and wall structure, indicating the diffusion of the hydrophilic molecule was controlled by short timescale adsorption/desorption processes onto the inner surface. In contrast, pH effects on D were less clear for relatively hydrophobic R123 and RB, suggesting the significant contributions of non-Coulombic interactions. Interestingly, the diffusion of these molecules in COOH-ONT 20nm was slower than in COOH-ONT 10nm . Slower diffusion in COOH-ONT20nm was attributable to relatively efficient partitioning of the hydrophobic dyes into the bolaamphiphile layers, which was reduced in COOH-ONT 10nm due to the stabilization of its layer by polyglycine-II-type hydrogen bonding networks. These results show that, by tuning the bolaamphiphile structures and their intermolecular interactions, unique environments can be created within the nanospaces for enhanced molecular separations and reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Modular Solar-to-Fuel Electrolysis at Low Cell Potentials Enabled by Glycerol Electrooxidation and a Bipolar Membrane Separator

Solar fuel generation through water electrolysis or electrochemical CO 2 reduction is thermodynamically limited when paired with the oxygen evolution reaction (OER). The glycerol electrooxidation reaction (GEOR) is an alternative anodic reaction with lower anodic electrochemical potential that utilizes a renewable coproduct produced during biodiesel synthesis. We show that GEOR on a Au-Pt-Bi ternary metal electrocatalyst in a model alkaline crude glycerol solution can provide significant cell potential reductions even when paired to reduction reactions in seawater and acidic catholytes via a bipolar membrane (BPM). We showed that the combination of GEOR electrooxidation and a BPM separator lowers the total cell potential by 1 V at an electrolysis current of 10.0 mA cm -2 versus to an anode performing OER when paired with hydrogen evolution and CO 2 reduction cathodes. The observed voltage reduction was steady for periods of up to 80 hours, with minimal glycerol crossover observed through the membrane. Furthermore, these results motivate new, high-performance cell designs for photoelectrochemical solar fuels integrated systems based on glycerol electrooxidation.

25 ENERGY STORAGE↗