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Modeling Electrolytic Conversion of Metabolic CO2 and Optimizing a Macrofluidic Electrochemical Reactor for Advanced Closed Loop Life Support Systems
The International Space Station (ISS) is currently equipped with a complex, heavy, and power consuming system that recovers approximately 50% of O2 from metabolic CO2. Future long duration missions will require a sustainable and highly efficient system capable of yielding a minimum of 75% O2 recovery. A Macrofluidic Electrochemical Reactor (MFECR) technology development effort is currently underway at NASA Marshall Space Flight Center (MSFC) to significantly increase current O2 recovery efficiency and reduce complexity of the system. This paper presents a comprehensive multi-physic 3D model developed at MSFC on CO2 conversion to O2 and C2H4 at standard conditions via MFECR. The 3D spatial domain of the model is a replica of the actual MFECR’s 3D drawing generated for the MFECR fabrication and operated to recover O2 from CO2 yielding C2H4 as byproduct. Electrochemical (EC) physics that includes EC multicomponent reaction mechanisms, mass transport, and current density distributions is coupled in the model with all the other physics phenomena involved in the process, such as free and porous fluid flow, multicomponent mass transfer, heat transfer, and DC electrical current generation along with Joule heating effect. The authors plan to use experimental results to validate this comprehensive and rigorous model and build a reliable simulator that will not only assist the authors on the MFECR design but also optimize its operation.
Modeling Electrolytic Conversion of Metabolic CO2 and Optimizing a Microfluidic Electrochemical Reactor for Advanced Closed Loop Life Support Systems
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Electron Transfer in Microemulsion-Based Electrolytes
The use of flowing electrochemical reactors, for example, in redox flow batteries and in various electrosynthesis processes, is increasing. This technology has the potential to be of central significance in the increased deployment of renewable electricity for carbon-neutral processes. A key element of optimizing efficiency of electrochemical reactors is the combination of high solution conductivity and reagent solubility. In this work, we show a substantial rate of charge transfer for an electrochemical reaction occurring in a microemulsion containing electroactive material is loaded inside the nonpolar (toluene) subphase of the microemulsion. The measured rate constant translates to an exchange current density comparable to that in redox flow batteries. The rate could be controlled by the surfactant, which maintains partitioning of reactants and products by forming an interfacial region with ions in the aqueous phase in close proximity. The hypothesized echanism is evocative of membrane-bound enzymatic reactions. Achieving sufficient rates of electrochemical reaction is the product of an effort designed to establish a reaction condition that meets the requirements of electrochemical reactors using microemulsions to realize a separation of conducting and reactive elements of the solution, opening a door to the broad use of microemulsions to effect controlled electrochemical reactions as steps in more complex processes.
Multiphysics Modeling of Electrode Dissolution under Hydrodynamic Conditions in Low Conductivity Water
Efficient plug-flow electrochemical reactors are characterized by their ability to effectively convert species with significant ionic strength and/or with the assistance of a well-behaved electrolyte. Because of the classic electroconductivity requirement, electrochemical reactors are not particularly attractive options for applications with low-conductivity conditions, especially for low-pressure feeds. However, these reactors can still find application in dedicated processes such as ultra-clean water conditioning and biological-coupled separation systems. Consequently, a multi-physics model was developed using COMSOL Multiphysics to characterize different reactor-design conditions based on the Tertiary Current Distribution which accounts for the effects of expected variations in electrolyte composition and ionic strength on the electrochemical process, as well as solution resistance and electrode kinetics. The modelling framework presented here employs single-phase laminar fluid flow, the Nernst-Planck equation, the water-based electroneutrality condition, and concentration-dependent overpotentials. This investigation particularly explores the electrolysis process of “anodic dissolution,” in which elemental species dissociate from the solid matrix of the electrode and enter the liquid phase of the electrolyte as soluble ions. The reactor configuration of interest has a rectangular parallel-electrode design and is operated galvanostatically. A series of parametric studies are carried out to inspect the response of the system when hydrodynamic, kinetic, and geometric conditions are changed. The parametric sweep resulted in variable effluent concentrations and system voltage, which reveal underlaying optimization patterns for electrode dissolution in low conductivity water.
Methods and systems for rebalancing electrolytes for a redox flow battery system
A rebalancing reactor for a redox flow battery system may include a first side through which hydrogen gas is flowed, a second side through which electrolyte from the redox flow battery system is flowed, and a porous layer separating and fluidly coupled to the first side and the second side, wherein, the hydrogen gas and the electrolyte are fluidly contacted at a surface of the porous layer, and a pressure drop across the second side is less than a pressure drop across the porous layer. In this way, rebalancing of electrolyte charges in a redox flow battery system may be performed with increased efficiency and cost effectiveness as compared to conventional rebalancing reactors.
Enabling microbial electrolysis cell scale-up via electrochemistry-, hydrodynamic-, and microbial ecology-informed framework
Microbial electrolysis cells (MECs) can produce green hydrogen while removing organic contaminants from liquid waste streams by leveraging the metabolic activity of electroactive microorganisms. Despite their potential in a sustainable, circular economy, large-scale MECs that can treat relevant volumes of wastewater have failed to deliver performance proportional to their lab-scale counterparts. The reason behind this lower performance at scale remains unclear. Here, in this study, we developed a combined electrochemistry-, hydrodynamic-, and microbial ecology-informed framework to analyze and optimize MEC performance during scale-up, enabling accurate quantification of major limitations and the identification of strategies to overcome them, ultimately facilitating equivalent performance at scale. Applying this framework to the scale-up of a zero-gap MEC from 9 cm 2 electrode area to 100 cm 2 electrode area, resulted in similar maximum current densities in a 100 cm 2 MEC (21.7 ± 1.1 A/m 2 ) compared to a 9 cm 2 system (25.1 ± 2.7 A/m 2 ), as well as equivalent hydrogen production rates of 69.3 L/L-d (100 cm 2 ) and 67.7 ± 2.4 L/L-d (9 cm 2 ). COMSOL flow dynamics simulations were used to scale up the reactor configuration without negatively affecting electrolyte velocity and distribution in the cell, minimizing the increase in internal resistances during scale-up (11.7 ± 0.5 mΩm 2 at 9 cm 2 ; 19.7 ± 1.3 mΩm 2 at 100 cm 2 ). Microbial community structures were assessed at both scales using high-throughput sequencing, highlighting the differences of populations across electrode dimensions and operational parameters. The framework presented here accelerates the development of effective strategies toward the scale-up of MECs by furthering the understanding of how electrochemical, hydrodynamic, and microbial ecology parameters change as the reactor dimension is increased. Ultimately, this approach contributes to advancing electrochemical biotechnology toward practical deployment in energy-efficient wastewater treatment systems.
Three-chamber electrochemical reactor for selective lithium extraction from brine
Efficient lithium recovery from geothermal brines is crucial for the battery industry. Current electrochemical separation methods struggle with the simultaneous presence of Na + , K + , Mg 2+ , and Ca 2+ because these cations are similar to Li + , making it challenging to separate effectively. We address these challenges with a three-chamber reactor featuring a polymer porous solid electrolyte in the middle layer. This design improves the transference number of Li + (t Li+ ) by 2.1 times compared to the two-chamber reactor and also reduces the chlorine evolution reaction, a common side reaction in electrochemical lithium extraction, to only 6.4% in Faradaic Efficiency. Employing a lithium-ion conductive glass ceramic (LICGC) membrane, the reactor achieved high t Li+ of 97.5% in LiOH production from simulated brine, while the concentrations of Na + K + , Mg 2+ , and Ca 2+ are below the detection limit. Electrochemical experiments and surface analysis elucidated the cation transport mechanism, highlighting the impact of Na + on Li + migration at the LICGC interface.
Insights into Active Sites and Mechanisms of Benzyl Alcohol Oxidation on Nickel–Iron Oxyhydroxide Electrodes
The electrochemical oxidation of bio-derived molecules has recently garnered interest for its potential in opening electrified synthetic pathways toward value-added products. Herein, we investigate the electrochemical conversion of benzyl alcohol (BA) to benzaldehyde and benzoate on nickel–iron (Fe ~ 7–18%) electrodes as a model system to understand reaction mechanisms and environmental conditions that can transform these molecules. Our results indicate a strong correlation between benzyl alcohol oxidation (BAO) onset potentials and Ni(II/III) redox peak positions, highlighting the potential role that lower oxidation states of nickel, i.e., Ni 3+ , can play in BAO catalysis. Our work on the Ni 2+/3+ system complements mechanisms that involve higher oxidation states of Ni as reported by others. We note that the Ni redox position and thus BAO onset is impacted by Fe incorporation during electrochemistry from unpurified electrolytes, which can resemble standard reactor operating conditions. We perform a systematic computational investigation into BAO and provide density functional theory (DFT) insights into how the redox mechanism has been such a prominent focus of alcohol oxidations. This includes the mode of BA adsorption and the nature of the adsorption site; upon conversion of the Ni 2+ surface to active Ni 3+ via hydroxyl deprotonation, BAO is thermodynamically downhill. Our DFT study also introduces the possibility of a vacancy-driven mechanism, though expected to be less prevalent during catalysis than the redox mechanism for a Ni 3+ surface. Through the systematic investigation of experimental reaction conditions and computational free energy thermodynamics, we have gained valuable insights into BAO reaction mechanisms that inform catalytic activity. Our study opens avenues for further design and development of catalyst active sites for the oxidation of related organic molecules.
Electrocatalytic Hydrogenation of Biomass-Derived Organics: A review
Sustainable energy generation calls for a shift away from centralized, high-temperature, energy-intensive processes to decentralized, low-temperature conversions that can be powered by electricity produced from renewable sources. Electrocatalytic conversion of biomass-derived feedstocks would allow carbon recycling of distributed, energy-poor resources in the absence of sinks and sources of high-grade heat. Selective, efficient electrocatalysts that operate at low temperatures are needed for electrocatalytic hydrogenation (ECH) to upgrade the feedstocks. For effective generation of energy-dense chemicals and fuels, two design criteria must be met: (i) a high H:C ratio via ECH to allow for high-quality fuels and blends, and (ii) a lower O:C ratio in the target molecules via electrochemical decarboxylation/deoxygenation to improve the stability of fuels and chemicals. The goal of this review is to determine whether the following questions have been sufficiently answered in open literature, and if not, what additional information is required: (1) What organic functionalities are accessible for electrocatalytic hydrogenation under a set of reaction conditions? How do substitutions and functionalities impact the activity and selectivity of ECH? (2) What material properties cause an electrocatalyst to be active for ECH? Can general trends in ECH be formulated based on the type of electrocatalyst? (3) What is the impact of reaction (electrolyte concentration, pH, operating potential) and reactor type conditions?
Electrolyte Takeover Strategy for Performance Recovery in Polysulfide-Permanganate Flow Batteries
The abundance of active material precursors for a polysulfide-permanganate flow battery makes it a compelling chemistry for large-scale, and potentially long-duration (>10 h), grid electricity storage. Precipitation, arising from either reactant crossover or electrolyte side reactions, decrease cell efficiencies during charge/discharge cycling. Regardless of the abundance and low cost of active materials, a system without high cyclability cannot meet grid electricity storage economic targets for applications that cycle regularly. Precipitated species can be removed, and reactor efficiency performance restored, by using an electrolyte takeover process, or ETP. Two ETP methods are investigated. One ETP uses the negative electrolyte, an alkaline polysulfide (pS) solution, as takeover solution, and another uses dilute acidic peroxide (DAP) as the takeover solution. Both ETPs maintain functional cell operation within an acceptable performance range over >1000 h and >200 cycles, a duration over which cells that do not undergo ETPs clog and fail. The DAP ETP proves especially effective and limits irrecoverable voltage efficiency fade below 0.02%/cycle. These ETPs, either individually, or in combination, can enable the requisite cyclability for practical polysulfide-permanganate flow battery systems.
Potential of electrolytic processes for recovery of molybdenum from molten salts for 99 Mo production
Molten salt reactor (MSR) technologies are receiving significant interest for commercialization because of their potential safety features and efficient energy production. In addition to producing reliable and clean energy, high-value radioisotopes could be harvested from MSRs as an additional revenue stream. Although significant quantities of 99 Mo will be produced in MSRs through fission, how accessible 99 Mo will be for direct recovery from a fuel salt is unclear. Electrolytic processes in fused salts have been used extensively for processing molten salts and have the potential to enable the extraction of 99 Mo directly from the fuel salt. This paper reviews the behavior of 99 Mo in the molten salt reactor experiment and summarizes theoretical aspects of the electrolytic process in high-temperature fused salt and the published experimental results on Mo extraction through electrolytic processes. Here, the general principle of fused-salt electrolytic processes is described, by electrodeposition of Mo with the following aspects: electrowinning, electrorefining, electroplating, and electroextraction with several experimental considerations. Finally, important considerations for recovery of 99 Mo from MSR relevant molten salts via electrodeposition are discussed.
Nuclear driven water decomposition plant for hydrogen production
The conceptual design of a hydrogen production plant using a very-high-temperature nuclear reactor (VHTR) to energize a hybrid electrolytic-thermochemical system for water decomposition has been prepared. A graphite-moderated helium-cooled VHTR is used to produce 1850 F gas for electric power generation and 1600 F process heat for the water-decomposition process which uses sulfur compounds and promises performance superior to normal water electrolysis or other published thermochemical processes. The combined cycle operates at an overall thermal efficiency in excess of 45%, and the overall economics of hydrogen production by this plant have been evaluated predicated on a consistent set of economic ground rules. The conceptual design and evaluation efforts have indicated that development of this type of nuclear-driven water-decomposition plant will permit large-scale economic generation of hydrogen in the 1990s.
Molten Salt Lattice Confinement Fusion (LCF) Fast Fission Reactor for Lunar and Planetary Surface Power
Molten salt fission reactors (MSR) have been suggested for lunar and planetary surface power systems. They have the advantage of operating at high temperature, for efficient thermal-electrical conversion, low pressure, long-lived with high nuclear fuel burnup. MSR are often designed to breed fissile 233U from natural 232Th by neutron capture and decay via: 232Th(n,)233Th(,)233Pa(,)233U Unfortunately, this process requires 233Pa isotope separation and segregation to decay to 233U. This requirement prevents additional neutron capture that interferes with 233U breeding. Instead, Wooley’s sub-critical, fast fission, molten salt reactor would use externally generated tokamak fusion neutrons1,2 to fission all actinides.We propose a simpler fusion-fast-fission sub-critical reactor that generates fast neutrons in situ from lattice confinement fusion (LCF) to fission fertile and fissile actinides. This hybrid reactor doesn't require enriched 235U fissile pins to initiate fis-sion reactions, nor 233Pa separation and segregation during operation. Like Wooley’s, this hybrid reactor “burns” natural uranium (238U) or thorium (232Th) which avoids uranium enrichment and additional fissile material launch safety and security costs. The LCF neutron source is initiated by bremsstrahlung photoneutrons (Fig. 1)3 or isotopic neutron sources in electron-screened lattices (Fig. 2)4,5. Alternatively, the electrolytic Pd-deuterium co-deposition6protocol fast fissions7 both 232Th and 238U. However, an aqueous electrolyte-based system, without pressurization similar to conventional pressurized water fission reactors, is incapable of high temperatures due to the boiling point of the electrolyte slightly over 100 C. Molten salts can be used instead as was demonstrated at the University of Hawaii8 using a variety of Ni and Pd cathodes in lithiated, hydrided and deuterated salts. These salts have melting points often exceeding 500C making them suitable to efficiently produce electrical power9 through either Advanced Stirling Genera-tors (< 100 kWe) or closed-Brayton Cycle (> 100 kWe). This hybrid reactor could power a wide range of lunar or Martian applications from unmanned in-struments, to charging vehicles and entire facilities such as human habitats or in situ resource utilization. The power conversion cycles are Carnot Cycle limited, but generally 30% efficient at best. However, waste heat on the moon or Mars is important to surviving either two-week lunar nights or Martian nights as well as providing process heat for mineral extraction and “living off the land”
Continuous-flow reactor with superior production rate and stability for CO 2 reduction using semiconductor photocatalysts
Semiconductor photocatalyst approaches for solar CO 2 reduction are attractive due to their simplicity but have lagged in efficiency compared to less-integrated photoelectrochemical (PEC) approaches and to electrolysis reactors. We identify poor mass transport and catalyst deactivation as key constraints. To address them, we have developed a continuous-flow photocatalytic reactor system allowing us to control the triple-phase interface on the photocatalyst surface using the liquid and reactant gas flow rates. With the goal of selectively producing CO, the reactor is optimized by controlling the pressure and flow rates of the reactant gas and electrolyte in contact with both sides with the intermediately placed catalyst. In comparison to batch reactors with an immobile photocatalyst bed and gas phase CO 2 or CO 2 purged water, 10–24 times higher production rates are achieved for photocatalysts such as TiO 2 , ZnO, C 3 N 4 , and CdS by simply changing to the designed flow-type photoreactor without any catalyst modification. In addition, CO selectivity (93.2%) and long-term stability (>780 min) using the designed reactor are significantly enhanced compared to using the batch reactors (71.7%, <180 min for reduced 50% activity). Here, we propose that the enhanced mass transport on the photocatalyst surface accelerates the desorption of the initial photolysis product, CO, and prevents the poisoning effect from deactivating photocatalyst activity. This study has the potential to facilitate the utilization of semiconductor-based photocatalytic reactions for achieving superior performance wih gaseous reactants.
Developing reactors for electrifying bio-methanation: a perspective from bio-electrochemistry
The integration of microbial synthesis with renewable electricity is an emerging route for both CO 2 utilization and seasonal energy storage in the form of stored bio-electrofuels. The major benefits of electrifying bioreactors include: using highly selective bio-catalysts for CO 2 conversion under mild reaction conditions; decoupling the production of more facile electrochemical intermediates, such as hydrogen, at the electrode from the production of bio-catalyzed multi-electron and/or carbon products, such as methane or acetate; using microbes as robust and self-regenerating catalysts enabling higher efficiency and durability in CO 2 conversion systems compared to inorganic catalysis. In this Perspective, we propose research aimed at developing electro-bioreactor components that will increase the productivity of the reactor while maintaining high energy efficiency and biocompatible reaction conditions to fully realize the benefits of electrified bioreactors. Furthermore, these developments include: flow reactors with tailored 3D electrodes to optimally use the reactor volume, electrocatalysts designed for peak performance in neutral pH electrolytes, high conductivity microbial media, and new membrane separator materials with high ion conductivity and low gas permeability. Production of methane via a hybrid electrical-biological approach is taken as a case study to motivate these developments. Finally, an iterative design–manufacture–test cycle, enabled by additive manufacturing and 3D printing technologies, is proposed to rapidly prototype components prior to large-scale manufacturing.
Advanced manufacturing for electrosynthesis of fuels and chemicals from CO 2
Advanced manufacturing (AM) represents an appealing approach for creating novel electrochemical systems for chemicals synthesis. In this work, we demonstrate AM for rapid development and testing for improved performance for the carbon dioxide reduction reaction across an evolution of vapor-fed reactor designs. In our final design, we observe activation- and mixed-control regimes for a variety of operating conditions via inlet CO 2 flow rate and electrochemical potential. Furthermore, we define a dimensionless number (Da) to identify mass transport regimes by exploring the impact of hypothesized underlying mass transport mechanisms, including consumption of CO 2 via OH - , increased local temperatures, and partial penetration of electrolyte into gas diffusion layer. The accelerated pace of reactor design and development led to high geometric current densities (500 mA cm -2 ), heightened selectivity (85.5% FE C 2+ products), and increased carbon dioxide conversion (16.6%) and cathodic energy efficiency (49.6% CO 2 R). Using AM vapor-fed reactors, we attain high ethylene (3.67%) and record ethanol (3.66%) yields compared to the literature. Finally, this work underscores the promise of AM for accelerating reactor design, understanding of governing phenomena, and improving the performance of catalytic systems.
Zirconium Sludge Criticality Calculations in Large Process Tanks
The Savannah River Site’s (SRS) H-Canyon recently re-activated its 6.3D electrolytic dissolver to dissolve stainless steel clad research reactor fuels from Japan. A potential new mission was identified to dissolve other long-cooled fuel stored at SRS that is not aluminum clad. In the basic process of dissolution, the spent fuel dissolves into nitric acid (bulk solution). The eight ft. high and four ft. radius 6.3D dissolver is unique in that it has a platinum-coated niobium insert to resist corrosion, and the niobium basket forms an anode and cathode arrangement within the charge chute (Fig 1,2). DC current flows from anode to cathode, at up to 10,000 amps at 45 volts, through the potential gradient in the nitric acid solution, which allows the stainless steel (or other non-aluminum cladding) of the fuel to dissolve.