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Initial results indicate that ionic liquids are promising media for the extraction of oxygen from lunar regolith. IL acid systems can solubilize regolith and produce water with high efficiency. IL electrolytes are effective for water electrolysis, and the spent IL acid media are capable of regeneration.
Understanding how modification of molecular structures changes the thermochemistry of H atom uptake can provide design criteria for the formation of highly active catalysts for reductive transformations. Herein, we describe the effect of doping an atomically precise polyoxotungstate with vanadium on proton-coupled electron transfer (PCET) reactivity. The Lindqvist-type polyoxotungstate [W 6 O 19 ] 2– displays reversible redox chemistry, which was found to be unchanged in the presence of acid, indicating an inability to couple reduction with protonation. However, the incorporation of a single vanadium center into the structure significantly changes the reactivity, and the potential required for one-electron reduction of [VW 5 O 19 ] 3– was shown to vary with the strength of the acid added. Construction of a potential-pK a diagram allowed assessment of the thermodynamics of H atom uptake, indicating BDFE(O–H) ≈ 64 kcal/mol, while chemical synthesis of the reduced/protonated derivative (TBA) 3 [VW 5 O 19 H] was used to probe the position of protonation.
Integrated photoelectrochemical (PEC) devices for water splitting represent a compelling pathway for sustainable hydrogen production, directly converting solar energy into chemical fuels. While alkaline systems have achieved state-of-the-art solar-to-hydrogen (STH) efficiencies above 20% using earth-abundant catalysts, acidic PEC architectures provide unique advantages for compact device integration, fast proton transport, and stable operation under highly dynamic solar conditions. Proton-exchange membrane (PEM)-based configurations enable high current densities, low gas crossover, and rapid ionic response, making them especially well-suited for intermittent, bias-free PEC operation, despite alkaline electrolysis being more technologically mature. A critical limitation of acidic PEC systems remains, the oxygen evolution reaction (OER), which currently relies on scarce and costly iridium catalysts, restricting scalability. Here, in this study, we report a series of low-iridium mixed-metal oxide catalysts synthesized via a surfactant-assisted borohydride reduction method. An optimized Ir 0.5 Ru 0.5 O x catalyst exhibits exceptional intrinsic activity (>400 A g –1 Ir at 1.55 V vs RHE) in 0.1 M HClO 4 and maintains stable operation for over 10 days in an integrated PEC flow-cell. Sustained hydrogen production is achieved at 1.65 V with a total iridium loading of only 0.1 mg cm –2 , substantially below commercial PEM benchmarks. These results demonstrate a viable pathway toward scalable, high-performance acidic PEC hydrogen technologies.
It is widely understood that the durability and reliability of polymer electrolyte membrane (PEM) water electrolyzers are heavily dependent on feedwater purity, with cation contaminants that originate from incomplete water purification and balance of plant materials significantly harming electrolyzer performance. However, contamination remains a challenge and a common cause of failure at the stack level, indicating the need for strategies to recover the performance of contaminated cells. In this study, we investigate the effects of temperature on the uptake, electrochemical impacts, and removal of contaminant calcium and iron cations. Lower operating temperatures increase the sensitivity of the cell performance to contaminant cations, while also decreasing cation uptake and promoting contaminant removal. Computational charge transfer modelling shows that lower temperature increases the concentration of contaminant at the cathode and facilitates their removal from the cell. By testing single cells under scenarios designed to mimic stack temperature dynamics, we investigate low-temperature operation as an approach to stack-relevant contaminant recovery. Together, these results demonstrate that the low-temperature recovery approach is a promising approach for acid-free contamination recovery for PEM water electrolysis to promote stack reliability and durability.
Commercial membrane electrolyzers rely on acidic fluorocarbon membranes and ionomers, requiring the use of expensive IrO x -based oxygen-evolution catalysts. Anion-exchange-membrane water electrolyzers (AEMWEs) operate in an alkaline environment, enabling the use of non-precious-metal catalysts. Here, we study and engineer CoO x -based catalyst-coated anodes deposited via hydrothermal synthesis directly onto porous transport layers both with and without thermal annealing. The self-supported, nanoneedle-structured Co3O4 anode, formed by annealing the as-synthesized cobalt carbonate hydroxide, Co(CO3) x (OH) y , outperforms the baseline Co3O4 nanoparticle ink-based anode in pure-water-fed AEMWE due to the improved catalyst-layer continuity and thus number of electroactive Co species. The as-synthesized and unannealed Co(CO3) x (OH) y , however, appears to undergo substantial conversion to a more-active CoO x (OH) y phase predominantly at the surface, with nominal Co3+ present and higher electrical conductivity, lowering the cell voltage to ∼200 mV at 1.0 A·cm–2 in pure-water-fed AEMWE compared to the conventional Co3O4 nanoparticle anodes. We analyze the differences in electrode electrochemical response between pure-water and KOH feed modes, finding distinct activation and degradation modes. The Co(CO3) x (OH) y anode shows significant activation and slower degradation linked to the conversion to oxyhydroxide. We propose catalyst layer designs that promote both hydroxide and electron transport, alongside interfacial engineering strategies to obtain high performance while mitigating anode degradation.
The status of the baselined shuttle fuel cell as well as the acid membrane fuel cell and space-oriented water electrolysis technologies are presented. The more recent advances in the alkaline fuel cell technology area are the subject of a companion paper. A preliminary plan for the focusing of these technologies towards regenerative energy storage applications in the multi-hundred kilowatt range is also discussed.
Palladium deposits were prepared by electrolysis for evaluation as catalytic materials. Electrolysis was carried out in acidic solutions consisting of either 1.0 M in NaCl and 0.01 M PdCl2 or 1.0 M NaCl and 0.04 M PdCl2. It was during the preparation of the palladium deposits that unexpected observations were made that led to the request for analytical services. The analyses did not, nor were they intended to, answer all of the questions. They did, however, shed light on the nature and magnitude of some of the contaminants in the solutions and in the palladium electrodes, as well as characterize the forms of the palladium deposits. Results of analyses are grouped into solution, deposit, and electrode categories for comparison purposes.
Limestone (calcite, CaCO 3 ) is an abundant and cost-effective source of calcium oxide (CaO) for cement and lime production. However, the thermochemical decomposition of limestone (~800 °C, 1 bar) to produce lime (CaO) results in substantial carbon dioxide (CO 2(g) ) emissions and energy use, i.e., ~1 tonne [t] of CO 2 and ~1.4 MWh per t of CaO produced. Here, we describe a new pathway to use CaCO 3 as a Ca source to make hydrated lime (portlandite, Ca(OH) 2 ) at ambient conditions (p, T) while nearly eliminating process CO 2(g) emissions (as low as 1.5 mol. % of the CO 2 in the precursor CaCO 3 , equivalent to 9 kg of CO 2(g) per t of Ca(OH) 2 ) within an aqueous flowelectrolysis/ pH-swing process that coproduces hydrogen (H 2(g) ) and oxygen (O 2(g) ). Because Ca(OH) 2 is a zero-carbon precursor for cement and lime production, this approach represents a significant advancement in the production of zero-carbon cement. The Zero CArbon Lime (ZeroCAL) process includes dissolution, separation/recovery, and electrolysis stages according to the following steps: (Step 1) chelator (e.g., ethylenediaminetetraacetic acid, EDTA)-promoted dissolution of CaCO 3 and complexation of Ca 2+ under basic (>pH 9) conditions, (Step 2a) Ca enrichment and separation using nanofiltration (NF), which allows separation of the Ca-EDTA complex from the accompanying bicarbonate (HCO 3 – ) species, (Step 2b) acidity-promoted decomplexation of Ca from EDTA, which allows near-complete chelator recovery and the formation of a Ca-enriched stream, and (Step 3) rapid precipitation of Ca(OH) 2 from the Ca-enriched stream using electrolytically produced alkalinity. These reactions can be conducted in a seawater matrix yielding coproducts including hydrochloric acid (HCl) and sodium bicarbonate (NaHCO 3 ), resulting from electrolysis and limestone dissolution, respectively. Careful analysis of the reaction stoichiometries and energy balances indicates that approximately 1.35 t of CaCO 3 , 1.09 t of water, 0.79 t of sodium chloride (NaCl), and ~2 MWh of electrical energy are required to produce 1 t of Ca(OH) 2 , with significant opportunity for process intensification. This approach has major implications for decarbonizing cement production within a paradigm that emphasizes the use of existing cement plants and electrification of industrial operations, while also creating approaches for alkalinity production that enable cost-effective and scalable CO 2 mineralization via Ca(OH) 2 carbonation.
KSC has spent many years researching Hollow Fiber Membrane Bioreactors as well as research encompassing:Alternate ammonia removal/Advanced oxidation. Brine purification technologies KSC-ISRU has built an electrolysis cell for the removal of acids in ISRU mining brines. Our goal is to combine all such technologies.
Ultraviolet irradiation of the n-type semiconductor TiO2 crystal electrode of an aqueous electrochemical cell evolves O2 at the TiO2 electrode and H2 at the Pt electrode. The gases are typically evolved in a 2:1 (H2:O2) volume ratio. The photoassisted reaction seems to require applied voltages, but values as low as 0.25 V do allow the photoassisted electrolysis to proceed. Prolonged irradiation in either acid or base evolves the gaseous products in amounts which clearly demonstrate that the reaction is catalytic with respect to the TiO2. The wavelength response of the TiO2 and the correlation of product yield and current are reported. The results support the claim that TiO2 is a true photoassistance agent for the electrolysis of water. Minimum optical storage efficiencies of the order of 1 percent can be achieved by the production of H2.
Zero-gap electrolyzers based on submicron thick proton-conducting oxide membranes (POMs) represent a promising approach to increasing the efficiency of H 2 production from water electrolysis while moving away from conventional perfluorosulfonic acid (PFSA) membranes. A critical barrier to the commercialization of such electrolyzers is that the ultrathin nature of POMs, which is necessary to achieve low cell resistance, makes them more susceptible to defects that can lead to unacceptably high rates of H 2 crossover. Herein, we demonstrate an approach to mitigate this problem through selective deposition of carbon-containing silicon oxide (SiO x C y ) “nanoplugs” into the defects of submicron thick SiO 2 membranes using a facile electrochemically mediated deposition process. Selective deposition of nanoplugs within the defects was verified by multiple characterization techniques, while scanning electrochemical microscopy (SECM) was used to confirm selective plugging of H 2 -crossover hotspots associated with defects at identical locations. Thanks to the use of nanoplugs, the H 2 permeance of 250 nm thick SiO 2 membranes was reduced by 5 to 6 orders of magnitude compared to the unmodified atomic layer deposition (ALD) SiO 2 membranes while having negligible impact on the ionic resistance of the membrane. These plug-modified membranes also enabled safe and stable operation of a zero-gap full cell electrolysis cell, in contrast to cells lacking nanoplugs that produced anode effluent streams having H 2 concentrations near or exceeding the lower flammability limit (LFL) of H 2 . Furthermore, beyond water electrolysis, this defect-sealing strategy has the potential to be broadly implemented in other applications, such as fuel cells and flow batteries, offering a versatile solution to mitigate crossover-related performance losses.
INTRODUCTION The Savannah River Site (SRS) is currently processing Fast Critical Assembly (FCA) fuel received from the Japan Atomic Energy Agency (JAEA) for disposition. Stainless steel-clad plate and rods in stainless steel containers are dissolved using electrolysis with a solution mixture of nitric acid (HNO3), potassium fluoride (KF), and gadolinium (Gd). An ion chromatography (IC) was developed and vetted to monitor fluoride at various sampling points of the process. To finalize the method, FCA test solution was analyzed to qualify the analytical method followed by real FCA process solution analysis using two different analytical columns. This presentation summarizes the development and vetting of the IC method.
A main goal in the field of In Situ Resource Utilization is to develop technologies that produce oxygen from regolith to provide consumables to an extraterrestrial outpost. The processes developed reduce metal oxides in the regolith to produce water, which is then electrolyzed to produce oxygen. Hydrochloric and hydrofluoric acids are byproducts of the reduction processes, which must be removed to meet electrolysis purity standards. We previously characterized Nation, a highly water selective polymeric proton-exchange membrane, as a filtration material to recover pure water from the contaminated solution. While the membranes successfully removed both acid contaminants, the removal efficiency of and water flow rate through the membranes were not sufficient to produce large volumes of electrolysis-grade water. In the present study, we investigated electrodialysis as a potential acid removal technique. Our studies have shown a rapid and significant reduction in chloride and fluoride concentrations in the feed solution, while generating a relatively small volume of concentrated waste water. Electrodialysis has shown significant promise as the primary separation technique in ISRU water purification processes.
A main goal in the field of In Situ Resource Utilization is to develop technologies that produce oxygen from regolith to provide consumables to an extratrrestrial outpost. The processes developed reduce metal oxides in the regolith to produce water, which is then electrolyzed to produce oxygen. Hydrochloric and hydrofluoric acids are byproducts of the reduction processes, which must be removed to meet electrolysis purity standards. We previously characterized Nation, a highly water selective polymeric proton-exchange membrane, as a filtrtion material to recover pure water from the contaminated solution. While the membranes successfully removed both acid contaminants, the removal efficiency of and water flow rate through the membranes were not sufficient to produce large volumes of electrolysis-grade water. In the present study, we investigated electrodialysis as a potential acid removable technique. Our studies have show a rapid and significant reduction in chloride and fluoride concentrations in the feed solution, while generating a relatively small volume of concentrated waste water. Electrodialysis has shown significant promise as the primary separation technique in ISRU water purification processes.
Although transition metal (M) alloying with platinum (Pt) is a promising approach to reduce the Pt dosage required in the hydrogen evolution reaction (HER), the catalytic activity and durability of PtM alloy are often unsatisfactory for acidic HER, especially at high currents, due to a reduced number of highly active sites (Pt) at the atomic level and challenges in stabilizing them to prevent detachment and aggregation. Herein, we report a robust functional structure integrated electrode (D-PtCu/CF) with abundant edge dislocations and very low platinum content (0.1 mg cm -2 ) to achieve high activity and stability in acidic HER within a proton exchange membrane water electrolysis cell (PEMWE). D-PtCu/CF exhibits high Pt mass activity (10.28 A mg Pt -1 ) and excellent operational stability (negligible decay after 200 h). X-ray absorption spectroscopy and in situ electrochemical experiments reveal that the lattice distortion caused by edge dislocations in PtCu mainly affects Pt atoms by compressing strain, reducing their ability to adsorb H. At the same time, Cu atoms are subjected to tensile strain, enhancing the bonding between Cu and H. Therefore, edge dislocations not only improve the intrinsic catalytic activity of Pt atoms but also increase the number of active sites (Cu) available for hydrogen adsorption, which synergistically accelerates the kinetics of the HER reaction. Finally, the PEMWE employing the D-PtCu/CF catalytic electrode can operate stably for 100 h at an industrial-level current density of 500 mA cm -2 with 1.63 V.
The production of oxygen on the Moon utilizing indigenous material is paramount to a successful lunar colonization. Several processes were put forth to accomplish this. The lunar liquid oxygen (LLOX) generation schemes which have received the most study to date are those involving: (1) the reduction of ilmenite (FeTiO3) by H2, C, CO, CH4, CO-Cl2 plasma; (2) magma electrolysis, both unadulterated and fluoride-fluxed, and (3) several others, including carbo-chlorination, HF acid leaching, fluorine extraction, magma oxidation, and vapor pyrolysis. The H2 reduction of ilmenite and magma electrolysis processes have received the most study to date. At this stage of development, they both appear feasible schemes with various pros and cons. However, all processes should be addressed at least at the onset of the considerations. It is ultimatley the energy requirements of the entire process, including the acquisition of feedstock, which will determine the mode of oxygen productions. There is an obvious need for considerably more experimentation and study. Some of these requisite studies are in progress, and several of the most studied and feasible processes for winning oxygen from lunar materials are reviewed.
Alkaline low temperature electrolysis (LTE) systems enjoy several potential advantages over acid-based LTE systems including facile oxygen evolution reaction (OER) kinetics and electrodes that can use little to no platinum group metals (PGM). The polymer membranes and membrane electrode assembly (MEA) structures going into alkaline electrochemical systems have seen significant advances in recent years. The objective of this project is to combine state-of-the-art alkaline polymer electrolyzer components into one optimized membrane electrode assembly (MEA) system to achieve DOE low temperature electrolysis (LTE) goals. The benefit of individual component advances cannot be fully appreciated until all aspects and components of the MEA are working at an equally high level of performance. New electrode fabrication methods were developed where solvent cast catalyst/ionomer solutions were used in place of insoluble ionomers to significantly improve adhesion. The membranes were improved in terms of durability and mechanical properties. The OER and HER catalysts were improved and made more durable.
Rare-earth elements (REEs) have been identified by NATO, the USDOE, and USGS as critical materials, i.e., materials which have significant demand yet pose supply-chain risks. Many of the existing processes for separations, metallization, and final parts production used across the REE supply chain involve energy intensive steps. For example, neodymium (Nd or NdPr) is produced using oxyfluoride electrolysis of Nd 2 O 3 , which requires hydrofluoric acid to produce a key electrolyte component (NdF 3 ) and generates undesired perfluorocarbon (PFC) gases. Such challenges make securing a resilient supply chain for NdFeB permanent magnets in countries like the United States prohibitively difficult. Here, we propose a chloride-based MSE process that circumvents these challenges, delivering high-purity NdPr from a (NdPr)Cl 3 feed from upstream REE separations. This eliminates environmentally-damaging steps of oxalate or carbonate precipitation and calcination, and enables superior production rates due to greater solubility of (NdPr)Cl 3 in chloride melts compared to Nd 2 O 3 . We show that CMSE generates high-purity NdPr (99.4 wt.%) while being energy-efficient (~ 6 kWh/kg-Nd). NdPr from CMSE was used to fabricate a NdFeB magnet with an excellent maximum energy product (> 40 MGOe), comparable to commercially available NdFeB magnets. This establishes CMSE as a leading approach for integrated, energy-efficient NdFeB magnet production.