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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 OSTI2020

Electrocatalytic hydrogenation of muconic acid

Various embodiments disclosed relate to electrocatalytic hydrogenation of muconic acid and polymers formed from the reaction products thereof. In various embodiments, the present invention provides an electrocatalytic method to prepare 3-hexene-1,6-dioic acid, 2-hexene-1,6-dioic acid, adipic acid, or a combination thereof, from muconic acid. The method includes passing current through a catalytic cathode in a reactor including an aqueous acidic solution including muconic acid, a supporting electrolyte, and an anode, so as to generate atomic hydrogen on the cathode surface in an amount effective to hydrogenate the muconic acid to yield a product including 3-hexene-1,6-dioic acid, 2-hexene-1,6-dioic acid, adipic acid, or a mixture thereof. Also disclosed is the polymerization of 3-hexene-1,6-dioic acid, 2-hexene-1,6-dioic acid, or a combination thereof with another compound, such as a diamine or a dialcohol, to form a polymer, such as a polyamide or a polyester.

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

Directly resolving surface vs. lattice self-diffusion in iron at the nanoscale using in situ atom probe capabilities

Surface self-diffusion studies on metals under elevated reaction conditions are limited, as it is inherently challenging to unambiguously follow atomic transport across highly-reactive surfaces. Here, quantitative and mechanistic insight into thermally induced atomic transport processes in bcc α-iron at the sub-nanometer level was achieved using isotopic tracer techniques coupled with in situ atom probe tomography (APT) capabilities. Specifically, using a reactor directly connected to the APT, needle-shaped specimens fabricated from epitaxial thin films with an embedded 57 Fe tracer layer were annealed in Ar at 500 °C and 350 °C for 1 hour. Furthermore, the tracer was positioned at various depths in the APT specimen by field evaporation, enabling targeted and simultaneous analysis of lattice and surface diffusion. 57 Fe concentration profiles reveal lattice self-diffusion occurs at 500 °C on the order of ~7 – 9 monolayers, while lattice diffusion is not resolvable at 350 °C. Considerable surface transport was, however, observed at both conditions, where atomic transport over the specimen surface led to the formation of a thin (≤1 nm), isotopically-intermixed layer at the surface. Further, the observed isotopic redistributions at 500 °C were convoluted by additional processes occurring in the subsurface, such as atomic intermixing in correlation with lattice diffusion. However, surface diffusion was determined to be the primary transport process at 350 °C and was thereby quantified. Ultimately, these results demonstrate the significance of surface self-diffusion as a short circuit pathway. More broadly, this approach has the potential to provide detailed insight into (self-)diffusion mechanisms across various materials while targeting site-specific reactions under elevated reaction conditions.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Optimization Modeling for Advanced Syngas to Olefin Reactive Systems

Reactor designs with mixed catalysts play an important role in transforming a multiple reactor system to single-shot reactors. In addition to savings in capital and ease of implementation, single-shot reactors are useful to break equilibrium limitations, thereby increasing the yield and selectivity of desired product as shown in previous studies. However, the nonlinear and highly exothermic nature of mixed-catalyst systems makes it difficult for commercial process simulation and optimization tools to optimize these systems. This study describes the development and application of optimization strategies for mixed-catalyst, single-shot reactors for syngas to olefin (STO) processes. Finding the optimal catalyst distribution is challenging and requires advanced solution strategies for singular optimal control problems, which are poorly conditioned and often lead to flat response surfaces. The graded bed and partial-moving finite-element approaches are used to find the optimal catalyst distribution that maximizes the olefins yield. A 1.3% increase in the yield is observed from one zone to three zones. The yield further improves from three zones to the exact infinite dimensional solution by 0.2%. This improvement can be realized in practice by changing only the catalyst distribution, without any extra investment. Lastly, the results suggest that a mixed-catalyst single shot reactor bed can be applied to other reaction mechanisms to increase reactor performance.

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

Long-Length SiC/SiC Tube Irradiation Experiment at LWR Temperatures Inserted into HFIR

This report describes the pre-irradiation characterization and successful assembly of a High Flux Isotope Reactor (HFIR) irradiation experiment designed to assess radiation-induced lateral bowing of silicon carbide fiber–reinforced, silicon carbide matrix composite (SiC/SiC) components under a radial fast neutron flux gradient at representative light-water reactor (LWR) temperatures of approximately 300 °C. The over-arching goal of this work is to validate thermomechanical models of SiC/SiC composite fuel assembly distortion used to predict the extent of lateral bowing and dose at which bowing reaches a maximum value. Ultimately, these models are used to ensure that fuel assembly distortion does not block coolant channels, interfere with control rod/blade movements, and/or impact local reactivity. The experiment contains six cladding tube specimens that are approximately 558.5 mm long with representative pressurized water reactor (PWR) outer and inner diameters of 9.5 mm and 7.5 mm, respectively. The specimens were thoroughly characterized prior to irradiation using traditional dimensional inspection and surface profilometry so that these measurements can later be compared with similar measurements that will be made post-irradiation to determine radiation-induced deformations. Furthermore, fine engraving markers were inscribed along the outer surfaces of the specimen and mapped using analytic photography and a three-dimensional stage. This technique allowed for accurate measurements of the marker spacings, which can be compared with similar measurements that will be made post-irradiation to provide local radiation-induced strain mapping. A light curtain optical micrometer was also employed to measure the pre-irradiation bowing of each specimen. The experiment was successfully assembled and inserted into position VXF-19 for HFIR cycle 516, which began May 12, 2026. The experiment will be removed after cycle 519, which is currently scheduled to end in December 2026.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2024

Using ethanol and isopropanol as biomass model compounds for understanding bond scission mechanisms over Cu/Mo 2 N catalysts

The conversion of biomass compounds into fuels and chemicals is an important step towards a more sustainable future. This work combines results from model surfaces and powder catalysts to demonstrate Cu-modified mo- lybdenum nitride (Cu/Mo 2 N) as a selective catalyst for dehydrogenation of the biomass model compounds, ethanol and isopropanol. Results from model surfaces showed that while Mo2N led to unselective decomposition via both dehydrogenation and dehydration, the addition of Cu increased the dehydrogenation activity and selectivity. DFT calculations showed how Cu influenced the structures of active sites, adsorbate interactions, and thus the product selectivity. Batch reactor studies on corresponding powder catalysts confirmed the trend that Cu modification increased dehydrogenation activity, and in situ X-ray absorption spectroscopy elucidated the Cu oxidation state under reaction conditions. Further, this work demonstrates a strategy for promoting dehydrogenation over Mo 2 N-based catalysts, as well as the feasibility of using model surfaces to guide the design of industrially relevant catalysts.

09 BIOMASS FUELS↗
DOE OSTI2021

NuScale Pressure and Temperature Limits Methodology Using Finite Element Analysis

Per 10 CFR 50 Appendix G, the pressure-temperature (P-T) limits curves and minimum temperature must be established to provide adequate margins for ferritic pressure-retaining components of the reactor coolant pressure boundary; this is to protect against brittle failure during any normal operating conditions, including anticipated operational occurrences and system hydrostatic tests, to which the pressure boundary may be subjected over its service lifetime. Specifically, ASME Code Section XI Appendix G procedures must be used for P-T limits calculation considering the pressure and temperature at various operating transient conditions. However, the elastic fracture mechanics solutions in Section XI are only suitable for cylindrical reactor pressure vessel (RPV) beltline without geometric discontinuities. Hence, these solutions are not suitable for postulated flaws near the core support blocks attached to the NuScale RPV inside surface, which is part of the beltline. As a result, NuScale has used finite element analysis to calculate thermal stress and stress intensity factor for the postulated flaws. The solutions using finite-element analysis have been validated using the formulations for straight cylinders for both axial and circumferential flaws. In addition, special considerations are given to the RPV beltline nil-ductility transition temperature (RTNDT) due to neutron irradiation occurring at lower temperatures than conventional plants. The paper summarizes the methodology and finite-element models used to develop P-T limits curves for NuScale RPV at the end of its 60-year design life.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2021

Experiments with a prototype titanium hot cavity surface ionization source intended for electromagnetic separation of radioactive samarium and other lanthanide elements

This paper reports experimental results of a prototype titanium surface ionization source. For the first time, a lanthanide ion beam has been produced with a surface ionizer composed completely of titanium metal. Titanium does not readily activate with neutron irradiation. This offers the potential for inserting an ion source made of titanium directly into a reactor with a pre-loaded non-radioactive lanthanide target. This seamlessly integrates target irradiation with isotope separation, eliminating post irradiation sample manipulation. Samarium ion beam currents up to 960 nA have been produced in an off-line test bench equipped with rudimentary beam optics. This is a crucial step toward the development of an ionization source adopted for the electromagnetic isotope separator (EMIS) facility, which has been designed for high throughput separations of radioactive 153 Sm and other lanthanides of interest in the field of nuclear medicine. The ion current and important factors affecting the performance of the ion source, such as the ionizer temperature and thermal gradient, are discussed. Lastly, the experimental results are presented together with a discussion of future modifications to optimize the overall surface ionization source performance.

07 ISOTOPE AND RADIATION SOURCES↗
DOE OSTI2021

Pulsed Thermal Tomography Nondestructive Examination of Additively Manufactured Reactor Materials and Components. Third Annual Progress Report

Additive manufacturing (AM) of high-strength corrosion resistance alloys for nuclear energy applications, such as stainless steel and Inconel, is currently based on laser powder bed fusion (LPBF) process. Some of the challenges with using LPBF method for nuclear manufacturing include the possibility of introducing pores into metallic structures. Probability of crack initiation at the pore depends on size, shape, and orientation of the defect. Pulsed Infrared Thermography Imaging (PIT) provides a capability for non-destructive evaluation (NDE) of sub-surface defects in arbitrary size structures. The PIT method is based on recording material surface temperature transients with infrared (IR) camera following thermal pulse delivered on material surface with flash light. The PIT method has advantages for NDE of actual AM structures because the method involves one-sided non-contact measurements and fast processing of large sample areas captured in one image. Following initial qualification of an AM component for deployment in a nuclear reactor, a PIT system can also be used for in-service nondestructive evaluation (NDE) applications. In this report, we describe recent progress in enhancing PIT capabilities in detecting microscopic subsurface defects in metals, and classifying shapes and orientation of pores in thermal images. For detection of microscopic defects in PIT imaging data, we have developed Spatial Temporal Denoised Thermal Source Separation (STDTSS) unsupervised machine learning (ML) image processing algorithm. We show that flat bottom hole (FBH) defects as small as 200µm in SS316 and IN718 specimens, can be detected with STDTSS algorithm. To the best of our knowledge, these are the smallest detected defects which are reported in literature. For classification of defects shapes, we have previously developed thermal tomography (TT) algorithm to obtain depth reconstructions of material defects from data cube of sequentially recorded surface temperatures. However, interpretation of TT images is non-trivial because of blurring with increasing depth. To address this challenge, we have developed a deep learning convolutional neural network (CNN) to classify size and orientation subsurface defects in simulated TT images.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2025

Technical Assessment of Off-Gas System Technologies for Potential Use in Molten Salt Reactors

Molten salt reactors (MSRs) are a class of Generation IV advanced reactor technologies aimed to enhance and improve the safety, fuel utilization and cost-effectiveness of nuclear power generation. MSR concepts are based on using a molten salt mixture as a primary nuclear reactor coolant, while the fuel can be either directly dissolved in the coolant (i.e., fluid-fueled) or can be in a separate solid form (i.e., salt-cooled solid-fueled). MSRs can be operated in either thermal or fast neutron spectra, as simple fissile convertors, or breeder reactors (e.g., utilizing both fissile and fertile fuels), as well as accelerator-driven sub-critical reactors or transuranic element burners. Operation of MSRs will necessitate management and treatment of the off-gas streams released to the headspace of the reactor where, in some designs, a cover gas can be circulated to remove certain fission products and maintain an inert atmosphere. An inert MSR cover gas swept over or sparged into the salt will confine radionuclides emerging from the free surface, including radioactive noble and non-noble gases, aerosols, and volatile species. The elements and compounds of these species will have a wide range of thermochemical and physical properties, some of which will decay to different products in the off-gas stream. Therefore, system components used to manage and treat MSR off-gas streams will need to be robust under dynamic reactor and chemistry conditions to support adequate reactor performance by managing the composition and species in the salt coolant and cover gas space. Off-gas system components would perform as a radionuclide boundary to the reactor vessel and a primary means for preventing radionuclide release; therefore, they are of high safety significance for MSR operations. This report reviews various technologies and materials for potential implementation in the design of an MSR off-gas system per a general conceptual framework. The reviewed technologies operate based on scrubbing, capture, delay, or separation of species in the off-gas stream. These include molten hydroxide scrubbers, solid sorbents, delay off-gas systems, particle traps, and cryogenic distillation. Since aspects of an off-gas system will be design-specific, the approach is to provide general discussions on attributes of these technologies and materials, including target off-gas stream species, operational parameters and conditions of importance to decontamination factors, implementation maturity, system component monitoring, potential off-normal conditions and considerations for waste products. The information aims to support the U.S. Nuclear Regulatory Commission in their safety evaluations for MSR designs.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2020

The passivity of low-temperature carburized austenitic stainless steel AISI-316L in a simulated boiling-water-reactor environment

The passive film on low-temperature-carburized AISI-316L austenitic stainless steel was studied in an oxygenated, simulated boiling-water-reactor environment with normal water chemistry. The microstructure was studied using scanning electron microscopy, grazing-incidence X-ray diffractometry, Auger electron spectroscopy, X-ray energy-dispersive spectroscopy, and transmission electron microscopy. For non-surface engineered AISI-316L, three distinct layers were observed after exposure: an outer layer of larger nickel-oxide enriched particles with the spinel structure, an intermediate layer of small Cr-oxide-enriched hematite particles, and a compact inner layer of Cr-enriched oxide also having the spinel structure. Exposure of low-temperature-carburized AISI-316L, in contrast, resulted in only two distinct layers. These layers did not include a compact Cr-rich inner layer. Instead, the innermost layer consisted of an oxide with the spinel structure that was a mixture of Fe, Cr and Ni oxide. The outer layer on the low-temperature-carburized specimen consisted of large loosely stacked particles with the spinel structure of mixed composition. In addition to passive-film characterization, the corrosion rate was studied by monitoring mass loss. Finally, after 500 h of immersion, the mass changes measured were relatively low for all specimens indicating good adhesion and low oxidation rates.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Advanced Fuels Campaign Time-at-Temperature Irradiation Campaign and Post-Irradiation Examination Plan

With increasing per capita energy consumption and rapidly growing energy consumption predicted for data centers, the US faces challenges in meeting projected energy demands. The current administration is attempting to accelerate the deployment of new nuclear construction by providing significant investments in advanced nuclear and by modernizing regulatory approaches for the licensing new reactors. However, enabling extended power uprates (EPUs) for the current nuclear reactor fleet would provide a shorter-term solution to better calibrate near-term energy generation capacity to the ever-growing energy demands of the modern era. One pathway to achieve power uprates is to increase the operational window by reassessing fuel safety limits around anticipated transients. Existing light-water reactors (LWRs) utilize a targeted operational window with well-defined operational efficiencies, yet this window is also often bound by conservative safety limits that result in suboptimal operational performance. For example, the operation of the existing fleet is highly constrained by safeguards to operation related to anticipated operational occurrences (AOOs), which are moderate-frequency transients expected with a frequency greater than 0.01 per reactor-year. These AOOs include temperature excursions where the critical heat flux for the system is exceeded, resulting in a departure from nucleate boiling (DNB) at the cladding surface. This DNB event is a thermohydraulic condition that, with current conservative fuel safety limits, results in the fuel rods being classified as “failed,” meaning that the cladding may not be returned to service.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2024

SCALE 6.3.1 Radiation Source Terms and Shielding Analysis for a Postulated Sodium-Cooled Fast Reactor Accident Scenario

In support of the US Nuclear Regulatory Commission non–light-water reactor fuel cycle demonstration project, SCALE 6.3.1 capabilities for radiation source term and shielding calculations are demonstrated for scenarios in the sodium-cooled fast reactor (SFR) fuel cycle. A postulated accident scenario, which consists of a seismic event causing the refueling machine to fall and release a spent fuel assembly inside the containment building (CB), is analyzed in this paper. Radiation source terms were generated for a U/TRU-10Zr metal fuel assembly with a 16.5% initial transuranic waste content and a discharge burnup of approximately 95 GWd/tHM; source terms were also generated for a high-assay low-enriched uranium metal fuel assembly (U-10Zr) with a 16.5% initial enrichment and a discharge burnup of 149.74 GWd/tHM. These radiation source terms were then used to determine the dose rate inside the CB and near the outer surface of the CB for a range of spent fuel assembly cooling times. The dose rate produced by the analyzed SFR assemblies is similar to that produced by a typical pressurized water reactor assembly with a discharge burnup of 50 GWd/MTU. Ultimately, the validation of the source terms predicted for SFRs with SCALE will need to be demonstrated via the use of assay measurements.

Radulescu, Georgeta↗
DOE OSTI2023

A review of in situ/operando studies of heterogeneous catalytic hydrogenation of CO 2 to methanol

Repurposing CO 2 into chemicals, one of the Carbon Dioxide Removal (CDR) strategies, still faces significant challenges in conversion and energy efficiency due to the lack of effective catalysts and processes. Fundamental understanding through in situ/operando investigations of the reaction mechanisms and catalyst structures is pivotal for developing the efficient catalysts. This paper reviews the past and recent in situ/operando studies of methanol synthesis from heterogeneous CO 2 hydrogenation over a few typical catalysts including Cu-based, oxide-based, and noble-metal-based catalysts. With the development of high-pressure reactors, in situ/operando IR, X-ray absorption spectroscopy (XAS), X-ray diffraction (XRD), neutron diffraction and imaging have been used to reveal the surface intermediates and structures of working catalysts under CO 2 hydrogenation conditions. On the one hand, the combined operando techniques shed light on working mechanisms for some catalytic systems. On the other hand, due to the complexity of selective CO 2 hydrogenation reaction and limited sensitivity of current accessible operando techniques to the surface structure of catalysts, it is still murky about the exact nature of the active sites at the surface/interface and how different sites promote different reaction paths. Furthermore, it is concluded that new methodologies for differentiating signals from different sites, and the development of surface-sensitive techniques for high pressure reactions are needed for providing structural descriptors of highly active and selective CO 2 conversion catalysts.

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

Microwave-driven heterogeneous catalysis for activation of dinitrogen to ammonia under atmospheric pressure

This paper presents an innovative approach to producing energy-dense, carbon–neutral liquid ammonia as a means for carrying energy. This approach synergistically integrates microwave reaction chemistry with novel heterogeneous catalysis that decouples dinitrogen activation from high-temperature and high-pressure reactions, altering reaction pathways and increasing ammonia formation rate. Results presented here demonstrate that ammonia synthesis can be conducted at 280 ? and ambient pressure to achieve ~1 mmol ammonia/g cat/h over supported ruthenium catalyst systems utilizing microwave irradiation. It is further shown that adding promoter ions such as potassium, cerium, and barium significantly improves the ammonia production rate over undoped ruthenium-based catalysts. This effect could be attributed to enhanced dielectric loss processes that lead to stronger microwave absorption by the catalyst. Measurement of the equilibrium constant under microwave conditions showed a higher ammonia yield than under thermal equilibrium conditions for both the iron- and ruthenium-based catalysts. Finally, this study also illustrates the advantages of using a variable-frequency microwave reactor for ambient-pressure ammonia synthesis. Mechanistically, investigators believed that the oscillating electric fields of the radiation can couple with adsorbed nitrogen on the surface and accelerate its dissociation. Since dinitrogen dissociation on the surface is rate limiting, this effectively accelerates the reaction.

Hu, Jianli (John)↗
DOE OSTI2020

Elucidating the Impact of Flow on Material-Sensitive Critical Heat Flux and Boiling Heat Transfer Coefficients: An Experimental Study with Various Materials

In this work, steady-state internal flow boiling critical heat flux (CHF) experiments were carried out at 10°C inlet subcooling and atmospheric pressure (84 kPa at an altitude of about 5300 feet) with mass flux ranging from 200 to 2,000 kg/m 2 -s on seven tube materials, including the accident-tolerant fuel cladding candidate FeCrAl (C26M) alloy. At a relatively low flow rate, the sensitivity of CHF to different materials was appreciable (the average difference among the tested materials was 19% at 200 kg/m 2 -s). As the absolute CHF differences stayed constant for higher flow rates, the increased flow rate led to reduced relative CHF differences among the tested materials (average relative difference of 15% at 1,000 kg/m 2 -s). FeCrAl alloy claddings that were oxidized under simulated Light Water Reactor (LWR) conditions yielded CHF comparable to as-received FeCrAl alloy cladding, with less than 1.8% difference. Experimental CHF results imply marginal material sensitivity impacts on the departure from nucleate boiling ratio in steady-state nuclear reactor cores. Yet, for accident progression analysis, material sensitivity may hold importance, as boiling behavior variation at low mass flux is appreciable. Macroscopic material parameters (surface wettability, surface roughness, and thermal properties) do not provide a suitable explanation for observed material-sensitive CHFs. Yet, surface roughness and thermal effusivity revealed power and linear relations, respectively, to the nucleate boiling heat transfer coefficients at low mass flux. At high mass flux, material sensitivity on nucleate boiling heat transfer significantly decreased due to the increased shear stress on boiling surface overwhelming material-related boiling implications.

36 MATERIALS SCIENCE↗
DOE OSTI2021

In Situ Identification of NNH and N 2 H 2 by Using Molecular-Beam Mass Spectrometry in Plasma-Assisted Catalysis for NH 3 Synthesis

In this work, ammonia synthesis at 533 K and atmospheric pressure was investigated in a coaxial dielectric barrier discharge (DBD) plasma reactor without packing and with porous γ-Al 2 O 3 , 5 wt % Ru/γ-Al 2 O 3 , or 5 wt % Co/γ-Al 2 O 3 catalyst particles. Gas-phase species were monitored in situ using an electron impact molecular-beam mass spectrometer (EI-MBMS). Gas-phase species NNH and N 2 H 2 were first identified under common conditions of plasma-assisted ammonia synthesis and were present at levels comparable to that of NH 3 in the plasma discharge. Concentrations of NNH, N 2 H 2 , and NH in a reactor packed with γ-Al 2 O 3 or other particles were lower than those observed in an empty reactor, while the concentration of NH 3 increased. These observations point to the importance of NNH and N 2 H 2 in plasma-assisted surface reactions in ammonia synthesis. Reaction pathways of direct adsorption of gas-phase NNH and N 2 H 2 on solid surfaces and subsequent reactions were proposed. This study demonstrated that in situ identification of gas-phase species via EI-MBMS provides a powerful approach to study the kinetics of plasmaassisted catalysis.

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

Modeling of ExB effects on tungsten re-deposition and transport in the DIII-D divertor

Mixed-material DIVIMP-WallDYN modelling, now incorporating ExB drifts, is presented that simultaneously reproduces tungsten (W) erosion and deposition patterns observed during the DIII-D Metal Rings Campaign, in which a toroidally symmetric set of W-coated tiles were installed in the carbon (C) DIII-D divertor. Since most reactor plasma facing component (PFC) designs call for mixed-material environments, including ITER’s W/Be enviroment, the divertor targets will quickly evolve into reconstitued surfaces of multiple elements. This work identifies controlling physics that affects material migration patterns in the divertor, which impact PFC lifetimes and impurity leakage from the divertor to the core. These simulations indicate that radial and poloidal ExB transport dominates over parallel force balance for high-Z impurities such as W in the divertor region of DIII-D. It is demonstrated that ExB drifts are required to reproduce the experimental observation of non-local W and C co-accumulation in a band ~7-9 cm outboard of the outer-strike-point (OSP) W source, for attached Lmode conditions in the unfavorable ion grad-B drift direction. In addition, W gross erosion is localized to the region outboard of the OSP, as the formation of C co-deposits suppresses W erosion at the strike point. Time-dependent simulations with scaled ExB impurity drifts (60% of the OEDGE-calculated drift velocity) and W re-erosion quantitatively reproduce these features, including depth-resolved W/C ratios, within a factor of 2 over ~115 seconds of accumulated plasma exposure. The location of co-deposition regions is shown to be well represented by an analytic leakage model, driven largely by poloidal ExB drifts. Qualitative agreement is also found between campaign-integrated W deposition measurements and simulations for the favorable ion grad-B drift direction, the standard mode of operation for most tokamaks. Furthermore, these results imply that a longterm inward radial migration of material from the outer divertor through the private flux region may occur in future devices.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2023

Cell Free and Immobilization Technologies (CFIT)

Today, several key factors negatively impact the production of fuels and chemicals from renewable sources. Common hindrances in the biological production of biochemicals are: (1) end-product or intermediate toxicity to the microbial biocatalyst, (2) the diversion of carbon to biomass formation, and (3) co-production of undesired byproducts. A particularly attractive alternative is to eliminate the biocatalyst entirely and instead operate the desired metabolic pathways in isolation, thus circumventing the roadblocks of biological toxicity, lower yields, and lack of specificity. However, cell-free enzyme systems still suffer from low productivities owing in part to the effects of free diffusion of intermediates, lack of long term enzyme stability, cofactor cost or inefficient recycling rates, and finally, the cost of enzyme production/purification. This project represents a new effort to propose innovative and cost competitive routes to producing biochemicals from a variety of feedstocks using cell free approaches. These routes will help reduce the current risk and cost associated with classical cell free production. Cell free technologies show promise for application to the production of toxic/inhibitory products or products difficult to separate from microbial growth media and can help reduce the production barriers in multiple areas of biological conversion of feedstocks to biochemicals. More specifically, we are developing new technologies and routes that could be used to produce high value biochemicals such as 2,3 BDO and terpenes (among many others) from biomass derived C5/C6 sugars or lignin but also from waste byproducts such as glycerol. This project will lead to significant innovation and also lead to new concepts and rational design of pathways and enzymes. Within this project, we will develop new metabolic enzyme cascades that will represent natural or artificial combinations of enzymes to produce the desired biochemicals from a variety of feedstocks. We are also developing basic design principals for constructing synthetic metabolons, using fusion proteins and synthetic protein scaffolds, to promote substrate channeling and stability while conserving peak activity. Additionally, our efforts include a techno economic analysis (TEA) of cell free approaches to provide the sensitivities of the process to enzyme loading, activity, pH, reactor volumes, cofactor recycling rates. Finally, we are focusing on further increasing stability, operating lifetime and efficiency of the pathway enzymes by immobilization on support surfaces. We are also focus on immobilizing pathway enzymes or combinations of enzymes on several different conducting polymers and evaluate the effect on stability and operating lifetime. As more combinations become available we will conduct a more systematic study of the means of immobilizing these enzymes. This preliminary work will enable the in-depth study of cofactor recycling at these interfaces using mediators for electron transfer. Taken together, these approaches will enable process intensification, continuous operation, lower capital and separations costs and end-product flexibility, and thus has the potential to contribute significantly to BETO's goals of cost competitive biofuels and bioproducts. To date we have demonstrated 1) the conversion of pyruvate to 2,3 BDO (4 enzymes with cofactor recycling, no additional cofactors needed) at >100g/L (>3g/L/h) using our enzyme tethering approach, 2) Generated mutants of a key redox enzyme with >180- fold improvement in NADH utilization over WT to >85% of NADPH utilization. 3) Produced mevalonate at >10g/L from glucose, limonene at >10g/L from mevalonate and more than >5g/L from glucose with crude enzyme preparations and complete cofactor recycling. 4) successfully generated fully active cross-linked aggregates (CLEAs) of NOX, a cofactor-regenerating water-forming oxidase that is key to our process with increased stability 5) Engineered and identified enzymes able to use the biomimetic cofactor NMN and synthesized new synthetic cofactors.

biocatalysis↗