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

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All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Machine learning for design principles for single atom catalysts towards electrochemical reactions

Machine learning (ML) integrated density functional theory (DFT) calculations have recently been used to accelerate the design and discovery of heterogeneous catalysts such as single atom catalysts (SACs) through the establishment of deep structure–activity relationships. Here, this review provides recent progress in the ML-aided rational design of heterogeneous catalysts with the focus on SACs in terms of structure–activity relationships, feature importance analysis, high-throughput screening, stability, and metal–support interactions for electrochemistry. Support vector machine (SVM), random forest regression (RFR), and deep neural networks (DNN) along with atomic properties are mainly used for the design of SACs. The ML results have shown that the number of electrons in the d orbital, oxide formation enthalpy, ionization energy, Bader charge, d-band center, and enthalpy of vaporization are mainly the most important parameters for the defining of the structure–activity relationships for electrochemistry. However, the black-box nature of ML techniques occasionally makes a physical interpretation of descriptors, such as the Bader charge, d-band center, and enthalpy of vaporization, non-trivial. At the current stage, ML application is limited by the lack of a large and high-quality database. Future prospects for the development of a large database and a generalized ML algorithm for SAC design are discussed to give insights for further studies in this field.

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

A combined SECM and electrochemical AFM approach to probe interfacial processes affecting molecular reactivity at redox flow battery electrodes

Redox flow batteries are attractive technologies for grid energy storage since they use solutions of redox-active molecules that enable a superior scalability and the decoupling of power and energy density. However, the reaction mechanisms of the redox active components at RFB electrodes are complex, and there is currently a pressing need to understand how interfacial processes impact the kinetics and operational reversibility of RFB systems. Here, we developed a combined electrochemical imaging methodology rooted in scanning electrochemical microscopy (SECM) and atomic force microscopy (AFM) for exploring the impact of electrode structure and conditioning on the electron transfer properties of model redox-active dialkoxybenzene derivatives, 2,5-di-tert-butyl-1,4-bis(2-methoxyethoxy)benzene (C1) and 2,3-dimethyl-1,4-dialkoxybenzene (C7). Using AFM and secondary-ion mass spectrometry (SIMS), we observed the formation of interfacial films with distinct mechanical properties compared to those of cleaved graphitic surfaces, and exclusively during reduction of electrogenerated radical cations. These films had an impact on the median rate and distribution of the electron transfer rate constant at the basal plane of multilayer and single layer graphene electrodes, displaying kinetically-limited values that did not yield the activation expected per the Butler–Volmer model with a transfer coefficient ~0.5. These changes were dependent on redoxmer structure: furthermore, SECM showed strong attenuation of C7 kinetics by a surface layer on MLG and SLG, while C1 kinetics were only affected by SLG. SECM and AFM results together show that these limiting films operate exclusively on the basal plane of graphite, with the edge plane showing a relative insensitivity to cycling and operation potential. Ultimately, this integrated electrochemical imaging methodology creates new opportunities to understand the unique role of interfacial processes on the heterogeneous reactivity of redoxmers at electrodes for RFBs, with a future role in elucidating phenomena at high active concentrations and spatiotemporal variations in electrode dynamics.

25 ENERGY STORAGE↗
DOE OSTI2022

A Heterogeneous Palladium Catalyst for the Polymerization of Olefins Prepared by Halide Abstraction Using Surface R 3 Si + Species

Abstract The silylium‐like surface species [ i Pr 3 Si][(R F O) 3 Al−OSi≡)] activates (N^N)Pd(CH 3 )Cl (N^N=Ar−N=CMeMeC=N−Ar, Ar=2,6‐bis(diphenylmethyl)‐4‐methylbenzene) by chloride ion abstraction to form [(N^N)Pd−CH 3 ][(R F O) 3 Al−OSi≡)] ( 1 ). A combination of FTIR, solid‐state NMR spectroscopy, and reactions with CO or vinyl chloride establish that 1 shows similar reactivity patterns as (N^N)Pd(CH 3 )Cl activated with Na[B(Ar F ) 4 ]. Multinuclear 13 C{ 27 Al} RESPDOR and 1 H{ 19 F} S‐REDOR experiments are consistent with a weakly coordinated ion‐pair between (N^N)Pd−CH 3 + and [(R F O) 3 Al−OSi≡)]. 1 catalyzes the polymerization of ethylene with similar activities as [(N^N)Pd−CH 3 ] + in solution and incorporates up to 0.4 % methyl acrylate in copolymerization reactions. 1 produces polymers with significantly higher molecular weight than the solution catalyst, and generates the highest molecular weight polymers currently reported in copolymerization reactions of ethylene and methylacrylate.

Gao, Jiaxin↗
NASA NTRS2001

Models of Small-Scale Patchiness

Patchiness is perhaps the most salient characteristic of plankton populations in the ocean. The scale of this heterogeneity spans many orders of magnitude in its spatial extent, ranging from planetary down to microscale. It has been argued that patchiness plays a fundamental role in the functioning of marine ecosystems, insofar as the mean conditions may not reflect the environment to which organisms are adapted. Understanding the nature of this patchiness is thus one of the major challenges of oceanographic ecology. The patchiness problem is fundamentally one of physical-biological-chemical interactions. This interconnection arises from three basic sources: (1) ocean currents continually redistribute dissolved and suspended constituents by advection; (2) space-time fluctuations in the flows themselves impact biological and chemical processes, and (3) organisms are capable of directed motion through the water. This tripartite linkage poses a difficult challenge to understanding oceanic ecosystems: differentiation between the three sources of variability requires accurate assessment of property distributions in space and time, in addition to detailed knowledge of organismal repertoires and the processes by which ambient conditions control the rates of biological and chemical reactions. Various methods of observing the ocean tend to lie parallel to the axes of the space/time domain in which these physical-biological-chemical interactions take place. Given that a purely observational approach to the patchiness problem is not tractable with finite resources, the coupling of models with observations offers an alternative which provides a context for synthesis of sparse data with articulations of fundamental principles assumed to govern functionality of the system. In a sense, models can be used to fill the gaps in the space/time domain, yielding a framework for exploring the controls on spatially and temporally intermittent processes. The following discussion highlights only a few of the multitude of models which have yielded insight into the dynamics of plankton patchiness. In addition, this particular collection of examples is intended to furnish some exposure to the diversity of modeling approaches which can be brought to bear on the problem. These approaches range from abstract theoretical models intended to elucidate specific processes, to complex numerical formulations which can be used to actually simulate observed distributions in detail.

McGillicuddy, D. J.↗
DOE OSTI2024

The Overlooked Potential of Sulfated Zirconia: Reexamining Solid Superacidity Toward the Controlled Depolymerization of Polyolefins

Closed-loop recycling via an efficient chemical process can help alleviate the global plastic waste crisis. However, conventional depolymerization methods for polyolefins, which compose more than 50% of plastics, demand high temperatures and pressures, employ precious noble metals, and yield complex mixtures of products limited to single-use fuels or oils. Superacidic sulfated zirconia (SZrO) with Hammet Acidity Functions (H 0 ) = -12 (i.e., stronger than 100% H 2 SO 4 ) is an industrially deployed heterogeneous catalyst capable of activating hydrocarbons under mild conditions and is shown to decompose polyolefins at ambient pressure and temperatures near 200 °C. Additionally, confinement of active sites in porous supports is known to radically increase selectivity, coking and sintering resistance, and acid site activity, presenting a possible approach to low-energy polyolefin depolymerization. However, a critical examination of the literature on SZrO led us to a surprising conclusion: despite 40 years of catalytic study, engineering, and industrial use, the surface chemistry of SZrO is poorly understood. Ostensibly spurred by SZrO's impressive catalytic activity, the application-driven study of SZrO has resulted in deleterious ambiguity in requisite synthetic conditions and insufficient characterization of acidity, porosity, and active site structure. Here, this ambiguity has produced significant knowledge gaps surrounding the synthesis, structure, and mechanisms of hydrocarbon activation for optimized SZrO, stunting the potential of this catalyst in olefin cracking and other industrially relevant reactions, such as isomerization, esterification, and alkylation. Toward mitigating these long extant issues, we herein identify and highlight these current shortcomings and knowledge gaps, propose explicit guidelines for characterization of and reporting on characterization of solid acidity, and discuss the potential of pore-confined superacids in the efficient and selective depolymerization of polyolefins.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Precision Structure Engineering of High-Entropy Oxides under Ambient Conditions

High-entropy oxides (HEOs) have unveiled a unique frontier in the realm of heterogeneous catalysis, taking advantage of the entropic effect and increased complexities to deliver ultrahigh stability and large tuning capability. However, current HEO synthesis mainly relies on high-temperature annealing approaches affording HEOs possessing no or low surface area, inferior active site exposure efficiency, and low controllability over the structure tuning. The grand challenge lies in producing high-quality HEO catalysts with high active site utilization efficiency, which relies on precision structure engineering, preferably under mild conditions. In this work, an in situ lattice engineering approach was developed to afford a supported HEO catalyst under ambient conditions. The HEO compositions (CuCoFeNiMnO x ) were uniformly integrated into the lattice of CeO 2 driven by cavitation-induced nucleation being generated via ultrasonication. The as-afforded catalysts were featured by high surface area, atomically dispersed HEO compositions, active redox properties, abundant oxygen vacancies (O V ), antiagglomeration, and high phase stability under harsh conditions. Compared with the ex situ introduction of HEO on the surface, the in situ method provides dual benefits to maintain the dispersity of HEO via entropic and lattice confinement effects. Engineering the complex HEO within the lattice of fluorite-structured CeO 2 also yields abundant defects (e.g., O V ) and active metal sites with strong reducing properties (e.g., Ce 3+ and Cu + ), which greatly improves the activity of the lattice oxygen and tunability of the adsorption behavior of the guest molecules, especially in the presence of impurities (e.g., water and propane). The catalytic performance of the supported HEO catalyst in oxidative procedures surpasses the pure dense phase HEO as well as the ex situ-generated catalysts. Further, the synthesis approach being developed in this work, together with the fundamental understanding in structure evolution and reaction mechanism, showcases a facile pathway under ambient conditions to generate stable catalysts capable of maintaining structural robustness in high-temperature conditions while delivering enhanced catalytic performance.

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

Numerical modeling of chemical looping oxidative dehydrogenation of ethane in parallel packed beds

Chemical looping oxidative dehydrogenation (CL-ODH) of ethane has the potential to be a highly efficient alternative to steam cracking for ethylene production. Accurate reactor modeling is of critical importance to efficiently scale up and optimize this new technology. This study reports a one-dimensional, heterogeneous packed bed model to simulate the CL-ODH of ethane to ethylene with a Na 2 MoO 4 -promoted CaTi 0.1 Mn 0.9 O 3 redox catalyst. Here, the overall reaction kinetics was well-described by coupling the gas-phase steam cracking of ethane with the reduction kinetics of the redox catalyst by H 2 and C 2 H 4 . The impact of H 2 on the formation rate of CO 2 byproduct from C 2 H 4 conversion was also thoroughly investigated to validate the applicability of the kinetic model under operational environments. The temperature variation within the different CL-ODH steps and the temperature distribution along the bed were also carefully considered. The accuracy of the model was validated by experiments conducted in a large lab-scale packed bed reactor (200 g catalyst loading), with an average deviation of 2.8% in terms of ethane conversion and ethylene yield. The model was subsequently used to optimize the operating parameters of the CL-ODH reactor, indicating that up to 63.7% single-pass C 2 +olefin yield can be achieved with the current redox catalyst bed whereas further optimization of the redox catalyst to inhibit C 2 H 4 activation can result in 69.4% single-pass C 2 +yield while maintaining low CO 2 selectivity.

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

Spectral Induced Polarization-Biogeochemical Relationships for Remediation Amendment Monitoring

Geophysical tools such as electrical resistivity (ER) can indirectly monitor subsurface changes in response to remedial injections. These methods exhibit relatively low spatial resolution compared to sediment core characterization but are advantageous due to the ability to collect measurements non-intrusively over time across large volumes of the subsurface. Moreover, along with confirmatory groundwater or core sampling, geophysical methods can be used during active biogeochemical remedies to monitor short-term contaminant transformations and mobility, as well as part of an overall strategy for long-term monitoring of subsurface contaminated sites. The use of alternating current spectral induced polarization (SIP) provides significantly more information than conventional geophysical methods like direct current ER. SIP allows for monitoring changes in both solution and surface conductivity by separation of real and imaginary conductivity, respectively, as well as surface capacitance. In principle, SIP can measure indicators of remedy progression such as precipitation reactions that sequester contaminants, potentially providing a better indication of amendment delivery and reactivity as compared to conventional ER methods. However, multiple processes and material properties have overlapping (interacting) electrical responses across a range of frequencies. Hence, the purpose of this scoping study was to evaluate if SIP can be used to monitor (a) amendment delivery and (b) precipitation and reactivity of amendments under consideration at Hanford. SIP measurements were collected in fully saturated columns packed with sand and Hanford formation sediments containing (a) amendments that were highly conductive with significant capacitance (zero valent iron – ZVI, sulfur modified iron – SMI) and (b) amendments that exhibited low electrical conductivity with a small capacitance (calcite, apatite, bismuth). The sand was a quartz material with homogenous particle size that exhibited a relatively low surface conductivity. It was used as a control for comparison with the sediments from the Hanford Site, which have a greater surface conductivity because of their complex mineralogy and heterogeneous particle size distribution and may have complex interactions with amendments. The amendment mass fraction was varied to represent the different stages and subsurface locations associated with the delivery of a remedy. The primary objective was to identify the solution and solid surface changes associated with the delivery amendments and their secondary reactions within the subsurface. The figure below summarizes results for the amendments tested through this project. The SIP phase shift or imaginary conductivity change for the high conductivity amendments was more than 10 times that of the low conductivity amendments, highlighting the relative ease of detection of ZVI and SMI independent of the background signal from sand or Hanford sediments. The ZVI phase shift and imaginary conductivity changes occur primarily at high frequency (> 100 Hz) whereas SMI changes were at low frequency (0.01 to 10 Hz). SIP signals of SMI also increased over time and the maximum shifted to lower frequencies. The low conductivity amendments (calcite, abiotic and biotic apatite, bismuth subnitrate) exhibited relatively small phase and imaginary conductivity changes when added to sediments. The changes were above minimum detection limits (0.5 mrad for phase shift, 0.03 µS/cm for imaginary conductivity) for the highest concentration except for the commercial bismuth material. The lowest amendment concentration that can be detected is likely sediment specific, as minerals in sediments (clays, magnetite, Fe-oxides) have some capacitance and, therefore, exhibit a variable phase shift.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2020

Multiple Degradation Mechanisms in Reinforced Concrete Structures, Modeling and Risk Analysis

The overarching goal of this project is to complement ongoing Department of Energy (DOE) Light Water Reactor Sustainability (LWRS)-funded Grizzly concrete modeling development efforts by providing improved multi-physics models for incorporation into the Grizzly and BlackBear codes. Objectives of this work identified at the outset of this project include: 1. Coupling between mechanical damage and transport processes. The mechanical damage will be characterized by nonlinear mechanical constitutive models appropriate for concrete used in nuclear power plants (NPPs). 2. Improved representation of the coupling among the transport process, building on the current moisture and thermal transport models in Grizzly. The parameters for coupling among heat and mass transport in the multi-physics model will be experimentally determined. 3. Coupling among different scale levels of concrete constituents, fine and coarse aggregates, cement paste, hydration products, and pore structure. 4. Probabilistic analysis of the random nature of the heterogeneous concrete structure and the environmental factors (ambient temperature and humidity) and their multiple effects on concrete deterioration. 5. Benchmark verification, validation and uncertainty quantification of the thermo-hygro- chemo-mechanical (THCM) concrete formulation. The end goal of this work was to provide a comprehensive and robust simulation capability that can be applied at the engineering scale for analysis of realistic deterioration scenarios in NPP concrete structures.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Nanostructures for Electrical Energy Storage (NEES) (2020 Final Technical Report)

Nanostructures for Electrical Energy Storage (NEES, www.efrc.umd.edu) was an Energy Frontier Research Center supported by the DOE Office of Science, Basic Energy Sciences, from 8/1/2009 to 7/31/2020. Led by the University of Maryland, NEES enjoyed extensive collaborations with its funded partners, including two DOE Laboratories and six universities. The NEES vision has been to reveal a set of scientific insights and design principles that can underpin a next-generation electrical energy storage approach, building on advances in nanoscale science and technology to achieve simultaneous high power and high energy over extended charge/discharge cycling. The vision is motivated by the recognition that scaling into the nano regime opens the door to new physical phenomena and that the tools enlisted in nanoscale research provide major new opportunities for the synthesis not only of materials at molecular scale but for structures at nano scale and above. NEES has translated this vision into its research program based on two observations. First, while the behavior of ions and electrons in electrolytes and in electrode materials is crucial to electrical energy storage (or more appropriately electrochemical energy storage), it is the transport of ion and electron charge between different structural components of a storage device that ultimately determine its performance. With it well recognized that the choice of electrode materials typically constrain ion transport kinetics as well as maximum ion concentration, the search for better electrode materials has been a primary driver of battery research. At the same time the synthesis of electrodes is typically based on aggregation of particles with varying size, shape, and orientation in the electrode. Together with the presence of additional materials to impart electrical conductivity and cohesion to the composite electrode, change in electrode materials is necessarily accompanied by structural changes at the nano/micro scale that are difficult to categorize and manage. From the beginning, NEES’ vision has been to create and study simpler, highly controlled spatial arrangements of known materials as battery components (electrodes, current collectors, and electrolyte) and to understand how design and structure above the molecular scale determines the energy storage performance available from known materials. Second, advances in nanoscience dramatically expanded the portfolio of synthesis methods, structural motifs, and new phenomena available for research. Some of these gave rapid access to new building blocks at the deep nanoscale (e.g., carbon nanotubes grown by self-assembly, nanoscale arrays formed by electrochemical self-alignment, monolayer films controlled by self-limiting reaction). Such advances served as the enabler for the NEES vision to be pursued experimentally through study of 3D structures created and controlled at the nano, micro, and meso scales. Here, we use meso as in the BES MESO Report, implying not only intermediate or varying length scales, but very much the way behavior is influenced by other factors including aggregation of nanocomponents at different densities and spatial configurations, statistical variations in the aggregates, hierarchical architectures in which they can be assembled, or local 3D configurations that result from the architectures. Over its life cycle, NEES has pursued two overarching goals: (1) to understand the scientific fundamentals of electrochemical storage from the nanoscale to the mesoscale; and (2) to create and learn from innovative, controlled, heterogeneous nanostructures, where such nanostructures can enable the first goal and serve as models for future paradigms in energy storage. Specific goals have included: Synthesize heterogeneous nanostructures comprised of multiple materials arranged in controlled fashion and characterize their behavior; Demonstrate and elucidate design principles for achieving simultaneous high power and high energy; Develop materials processes which enable precision control of thin layers and 3D structures; Investigate the impact of artificial interphases on electrode stability during ion insertion/deinsertion; Create dense arrays of nanostructures to understand how the architecture of these assemblies, along with nanostructure design, influences energy storage behavior at the mesoscale; Identify and understand the consequences of nanoconfinement and local inhomogeneities in 3D mesoscale arrays; Develop and apply computational models to stimulate, guide and interpret experiments.

25 ENERGY STORAGE↗
NASA NTRS2013

Supercritical Water Mixture (SCWM) Experiment in the High Temperature Insert-Reflight (HTI-R)

Current research on supercritical water processes on board the International Space Station (ISS) focuses on salt precipitation and transport in a test cell designed for supercritical water. This study, known as the Supercritical Water Mixture Experiment (SCWM) serves as a precursor experiment for developing a better understanding of inorganic salt precipitation and transport during supercritical water oxidation (SCWO) processes for the eventual application of this technology for waste management and resource reclamation in microgravity conditions. During typical SCWO reactions any inorganic salts present in the reactant stream will precipitate and begin to coat reactor surfaces and control mechanisms (e.g., valves) often severely impacting the systems performance. The SCWM experiment employs a Sample Cell Unit (SCU) filled with an aqueous solution of Na2SO4 0.5-w at the critical density and uses a refurbished High Temperature Insert, which was used in an earlier ISS experiment designed to study pure water at near-critical conditions. The insert, designated as the HTI-Reflight (HTI-R) will be deployed in the DECLIC (Device for the Study of Critical Liquids and Crystallization) Facility on the International Space Station (ISS). Objectives of the study include measurement of the shift in critical temperature due to the presence of the inorganic salt, assessment of the predominant mode of precipitation (i.e., heterogeneously on SCU surfaces or homogeneously in the bulk fluid), determination of the salt morphology including size and shapes of particulate clusters, and the determination of the dominant mode of transport of salt particles in the presence of an imposed temperature gradient. Initial results from the ISS experiments will be presented and compared to findings from laboratory experiments on the ground.

salts↗
DOE OSTI2023

Electric Field Effects on Water and Ion Structure and Diffusion at the Orthoclase (001)–Water Interface

Understanding the electrochemical properties of mineral–water interfaces tends to rely upon electrical double layer (EDL) models, but these models are based on the assumption that electrostatic equilibrium is constantly maintained. In reality, interfacial reactions, ion diffusion, and their electrochemical signatures are based in nonequilibrium conditions of locally or globally imbalanced electrical fields where current EDL models have limited purview. In this work, we performed molecular dynamics (MD) simulations of the orthoclase (001) surface in contact with a 1 M NaCl aqueous solution under various electric fields, to explore the interplay between EDL structure and dynamics when perturbed by electric fields of different direction and strength, by confinement, and by different distributions of structural surface charge. The simulations showed that confinement between two opposing (001) surfaces led to the development of an induced field when the applied field was perpendicular to the surfaces and, as a result, to ionic diffusion coefficients that were independent of electric field strength. In contrast, when the applied field was parallel to the surfaces, confinement resulted in ionic diffusion coefficients that were more strongly dependent on the magnitude of the electric field than in bulk water. Differences in the density and distribution of aluminol groups on the two surfaces had a significant impact on how the interfacial structure and dynamics varied in the presence of an electric field. Notably, these differences resulted in an electro-osmotic flow with opposite directions at the two surfaces under parallel applied electric field. Overall, the MD simulations highlighted the importance of considering atomic-level structure and heterogeneities when developing models of the electrochemical properties of mineral–water interfaces.

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

Gas-Liquid Flow Modeling for Renewable Fuels Production

Aerobic/anaerobic and gas fermentation pathways have emerged as promising new technologies for the generation of renewable fuels/chemicals from biomass derived sugars, and mixtures of greenhouse/energy rich gas streams (CO2/CH4/H2/CO) via microbial action. Example pathways include sugars-to-ethanol conversion, biomethanation (CO2/H2 to CH4), biogas upgrading, CO fermentation and wet-waste conversion. Gas and liquid phase transport, mass-transfer, and mixing physics at large length scales can significantly affect microbial conversion rates, particularly when the microbial reaction requires a narrow set of conditions. These phenomena are difficult to study in small-scale bench-top reactors that are typically well-mixed. Predictive computational fluid dynamics (CFD) based simulations can therefore aid in the scale-up, design and optimization of these reactors. This work presents multiphase Euler-Euler CFD simulations of at-scale (~500 m3) bioreactors. Our mathematical model treats the gas and liquid as interpenetrating phases. This approach reduces the computational complexity of tracking individual gas bubbles that are several orders of magnitude smaller than reactor dimensions. We solve the Reynolds averaged Navier-Stokes (RANS) multiphase equations that account for phase and chemical species transport, interphase mass and momentum transfer and uses a phenomenological model for gas uptake by microbes. We use a customized solver derived from open-source CFD toolbox, OpenFOAM [1], to perform these simulations, which has been validated against small-scale reactors in our previous work [2]. There is currently a knowledge-gap regarding bubble-size distributions when using gas mixtures with vastly different properties, which can have a significant impact overall mass-transfer. For example, hydrogen bubbles are more buoyant compared to other relatively heavier gases (CO2/CH4/CO), resulting in a large distribution of residence times and bubble sizes. This work therefore develops a deeper understanding of bubble dynamics and interphase mass transfer in such heterogenous gas mixtures through well-resolved computational models. We use a population balance model (PBM) for bubble-size-distribution modeling that is validated against small-scale experiments in our solver with an uncertainty quantification study for bubble coalescence and break-up model parameters. Results pertaining to multiple simulations of gas-fermentation reactors are presented where gas mixtures with varying compositions of CO2/CH4/CO/H2 are imposed at the sparger boundaries. The spatio-temporal variations in bubble-size distribution and mass transfer coefficient are analyzed for varying superficial velocities and gas-compositions for varying sizes of bubble-column and airlift reactors. This work will also examine the performance of different reactor designs, viz. bubble column reactor, airlift reactor with an internal draft tube, and a stirred-tank reactor with Rushton impellers. Reactor mass-transfer coefficient, gas hold-up, and dissolved gas distribution are critically analyzed among reactors, and sensitivity studies pertaining to gas flow rates and reactor geometry will be presented. [1] Weller, H., Tabor, G., Jasak, H. and Fureby, C., A tensorial approach to computational continuum mechanics using object-oriented techniques, Computers in physics, 12, 6, 620--631, 1998. [2] Rahimi, M., Sitaraman, H., Humbird, D. and Stickel, J., Computational fluid dynamics study of full-scale aerobic bioreactors: Evaluation of gas-liquid mass transfer, oxygen uptake, and dynamic oxygen distribution, Chemical Engineering Research and Design, 139: 283-295.

BIOMASS FUELS↗
DOE OSTI2020

Catalytic Hydrogen Production from Methane: A Review on Recent Progress and Prospect

Natural gas (Methane) is currently the primary source of catalytic hydrogen production, accounting for three quarters of the annual global dedicated hydrogen production (about 70 M tons). Steam–methane reforming (SMR) is the currently used industrial process for hydrogen production. However, the SMR process suffers with insufficient catalytic activity, low long-term stability, and excessive energy input, mostly due to the handling of large amount of CO 2 coproduced. With the demand for anticipated hydrogen production to reach 122.5 M tons in 2024, novel and upgraded catalytic processes are desired for more effective utilization of precious natural resources. In this review, we summarized the major descriptors of catalyst and reaction engineering of the SMR process and compared the SMR process with its derivative technologies, such as dry reforming with CO 2 (DRM), partial oxidation with O 2 , autothermal reforming with H 2 O and O 2 . Finally, we discussed the new progresses of methane conversion: direct decomposition to hydrogen and solid carbon and selective oxidation in mild conditions to hydrogen containing liquid organics (i.e., methanol, formic acid, and acetic acid), which serve as alternative hydrogen carriers. We hope this review will help to achieve a whole picture of catalytic hydrogen production from methane.

08 HYDROGEN↗
NASA NTRS1998

Stratospheric Sulfuric Acid and Black Carbon Aerosol Measured During POLARIS and its Role in Ozone Chemistry

Stratospheric aerosol can affect the environment in three ways. Sulfuric acid aerosol have been shown to act as sites for the reduction of reactive nitrogen and chlorine and as condensation sites to form Polar Stratospheric Clouds, under very cold conditions, which facilitate ozone depletion. Recently, modeling studies have suggested a link between BCA (Black Carbon Aerosol) and ozone chemistry. These studies suggest that HNO3, NO2, and O3 may be reduced heterogeneously on BCA particles. The ozone reaction converts ozone to oxygen molecules, while HNO3 and NO2 react to form NOx. Finally, a buildup of BCA could reduce the single-scatter albedo of aerosol below a value of 0.98, a critical value that has been postulated to change the effect of stratospheric aerosol from cooling to warming. Correlations between measured BCA amounts and aircraft usage have been reported. Attempts to link BCA to ozone chemistry and other stratospheric processes have been hindered by questions concerning the amount of BCA that exists in the stratosphere, the magnitude of reaction probabilities, and the scarcity of BCA measurements. The Ames Wire Impactors (AWI) participated in POLARIS as part of the complement of experiments on the NASA ER-2. One of our main objectives was to determine the amount of aerosol surface area, particularly BCA, available for reaction with stratospheric constituents and assess if possible, the importance of these reactions. The AWI collects aerosol and BCA particles on thin Palladium wires that are exposed to the ambient air in a controlled manner. The samples are returned to the laboratory for subsequent analysis. The product of the AWI analysis is the size, surface area, and volume distributions, morphology and elemental composition of aerosol and BCA. This paper presents results from our experiments during POLARIS and puts these measurements in the context of POLARIS and other missions in which we have participated. It describes modifications to the AWI data analysis procedures in which the collection of BCA is modeled as a fractal aggregate. The new analysis results in an increase in BCA surface area of approximately 24 and an increase in mass of 7-10 from the previous method. For the current study, BCA surface area is used in computer models that attempt to predict measured NOx/NOy ratios and O3 depletion rates. Inclusion of the HNO3 reaction with BCA in one model tends to improve the agreement of calculated to measured NOx/NOy ratio. However, it was found that these trends are viable only if the reactions are catalytic.

Strawa, Anthony W.↗
DOE OSTI2025

Atomically Dispersed Ni‐N‐C Catalysts for Electrochemical CO 2 Reduction

Abstract The atomic dispersion of nickel in Ni‐N‐C catalysts is key for the selective generation of carbon monoxide through the electrochemical carbon dioxide reduction reaction (CO 2 RR). Herein, the study reports a highly selective, atomically dispersed Ni 1.0% ‐N‐C catalyst with reduced Ni loading compared to previous reports. Extensive materials characterization fails to detect Ni crystalline phases, reveals the highest concentration of atomically dispersed Ni metal, and confirms the presence of the proposed Ni‐N x active site at this reduced loading. The catalyst shows excellent activity and selectivity toward CO generation, with a faradaic efficiency for CO generation (FE CO ) of 97% and partial current density for CO (j co ) of ‐9.0 mA cm −2 at ‐0.9 V in an electrochemical H‐type cell. CO 2 RR activity and selectivity are also studied by rotating disk electrode (RDE) measurements where transport limitations can be suppressed. It is expected that the utility of these Ni‐N‐C catalysts will lie with tandem CO 2 RR reaction schemes to multi‐carbon (C 2+ ) products.

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

Influence of physical and chemical hydrology on bioremediation of a U-contaminated aquifer informed by reactive transport modeling incorporating 238 U/ 235 U ratios

Microbially-catalyzed reductive immobilization of aqueous uranium (U) as a solid phase has been proposed as a U remediation technique. Both laboratory and field experiments have demonstrated that this reduction reaction alters the 238 U/ 235 U ratio, producing a 238 U-enriched U(IV) solid. In contrast, other major U reactive transport processes fractionate these isotopes much less. This suggests the potential to quantify the extent of bioreduction occurring in groundwater containing U using the 238 U/ 235 U ratio, which would substantially improve upon current practices largely relying on U concentration measurements alone. Current reactive transport models for uranium dynamics include only concentration measurements, which are strongly influenced by highly coupled reactive transformation and aqueous transport processes. The complex physical and chemical behavior of U potentially compromises such quantitative analysis of U storage and release. Here we report the first numerical reactive transport model which explicitly incorporates variations in the 238 U/ 235 U ratio of U and demonstrates improved interpretation of the principal chemical reactions and groundwater transport processes affecting the subsurface mobility and distribution of this widespread contaminant. Recent U bioreduction studies performed in a contaminated aquifer in Rifle, Colorado, USA applied Rayleigh distillation models to interpret U stable isotope fractionation observed as a result of acetate amendment. These simplified models were unable to resolve the spatiotemporal pattern of U isotope fractionation recorded in the aqueous solutes. Here, we employ the multi-component, isotope-enabled CrunchTope reactive transport software to interpret these measured U isotope ratios, and demonstrate accurate reproduction of observed trends in both geochemistry and 238 U/ 235 U ratios for two consecutive years of field experiments. Overall, our results indicate that accurately modeling both the U concentration and isotope ratio distributions greatly constrains the parameter space of the model. We find that the transport properties of U in the Rifle aquifer are governed by the presence of low-permeability regions, which the isotopes are uniquely sensitive to. When U reduction is spatially constrained by these low-permeability regions, the shift in the 238 U/ 235 U ratio becomes more muted. Accurate modeling of observed U isotope ratios thus provides a powerful means to better understand bioremediation, and the current study serves to advance the application of this novel method.

238U/235U↗
NASA NTRS1995

Soot Aerosol In The Atmosphere: Pole-to-Pole Distribution And Contributions by Aircraft

Interest in the distribution of black carbon (soot) aerosol (BCA) in the atmosphere is warranted for the following reasons: (1) BCA has the highest absorption cross section of any compound known, thus it can absorb solar radiation to cause atmospheric warming; (2) BCA is a strong adsorber of gases, thus it can catalyze heterogeneous chemical reactions to modify the chemical composition of the atmosphere; (3) If aircraft emission is the major source of atmospheric BCA, it can serve as an atmospheric tracer of aircraft exhaust. We collect BCA particles greater than or equal to 0.02 micrometer diameter by wires mounted on both the DC-8 and ER-2 aircraft. After return to the laboratory, the wires are examined with a field emission scanning electron microscope to identify BCA particles by their characteristic morphology. Typically, BCA exists in the atmosphere as small particles of complex morphology. The particle sizes at the source are measured in tens of Angstrom units; after a short residence time in the atmosphere, individual particles coalesce to loosely packed agglomerates of typical dimensions 0.01 to 0.1 micrometer. We approximate the size of each BCA aggregate by that of a sphere of equivalent volume. This is done by computing the volume of a sphere whose diameter is the mean between averaged minimum and maximum dimensions of the BCA particle. While this procedure probably underestimates the actual surface area, it permits us to compare BCA size distributions among themselves and with other types of aerosols. When statistically justified, we fit lognormal distributions to the data points to determine number concentrations, geometric mean radii, standard deviations, BCA surface areas and volumes. Results to date permit the following conclusions: (1) BCA concentration in the northern stratosphere averages 0.6 ng per cubic meters. This amount is one part in 10(exp 4) after a volcanic eruption (e.g., Pinatubo) increasing to about one percent during volcanic quiescence. In the northern troposphere, BCA concentration averages 3.2 ng per cubic meters, or 0.3 percent of the background aerosol. (2) Applying an BCA emission index EI(BCA)=5 x 10(exp -5), measured in the exhaust wake of a Concorde supersonic jet aircraft, to realistic estimates of fuel burnt by the current and projected fleets permits us to conclude that: (i) Most BCA in the northern stratosphere results from aircraft emissions; (ii) Most BCA in the northern troposphere results from other sources than aircraft; (iii) A projected supersonic fleet will increase the northern stratospheric BCA concentration by one order of magnitude, unless the emission index is substantially reduced. (3) A strong gradient between the northern and southern hemispheres indicates that mixing across the equator is greatly inhibited in relation to atmospheric residence times of BCA. (4) The single scatter albedo of BCA/"background" aerosol mixtures suggests a cooling effect for most of the globe; an exemption is the Arctic because of the high surface albedo of the snow/ice covered earth's surface.

Pueschel, R. F.↗