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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 OSTI2023

Thermochemical processes for CO 2 hydrogenation to fuels and chemicals: Challenges and opportunities

This manuscript discusses the potential use of CO 2 as a carbon and oxygen carrier to return it to the carbon life cycle in the form of fuels or chemicals via thermochemical catalytic pathways. Theoretically, CO 2 hydrogenation can form a variety of fuels and chemicals. Practically, however, the selectivity, conversion, operating range, and kinetic limitations and operational cost determine the end product. Because of their high value and versatility as a chemical or fuel, small olefins (i.e., C 2 H 4 ) and methanol are often considered as target species. Whether alcohol or olefin formation, CH 4 and CO are the nature’s primary choices of CO 2 conversion. They can be formed over a wide operating temperature, pressure, and CO 2 :H 2 ratios. They are often competitive carbon species in olefin or methanol formation steps. Although they are less valuable as end products, they can be used as intermediate species. Secondary processes of CO and CH 4 to form chemicals and fuels can increase the overall CO 2 hydrogenation yield. Independent of the choice of end product, CO 2 hydrogenation requires hydrogen. Pure hydrogen derived mostly from fossil fuels adds to the overall process cost and also increases the CO 2 emissions. Hydrogen produced from water electrolysis is a renewable green pathway but is limited by the process efficiency and cost. As an alternative to pure hydrogen, low-value, small chain paraffins are suggested as the hydrogen carriers. Carbon dioxide–assisted oxidative dehydrogenation of paraffins to olefins process is a direct pathway to olefin formation. The paper discusses these potential pathways for CO 2 utilization based on theoretical analysis and recent advances in academia and industry.

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

Performance and cost analysis of liquid fuel production from H 2 and CO 2 based on the Fischer-Tropsch process

Electro-fuels can be produced from concentrated sources of carbon dioxide and hydrogen using electricity generated from renewable sources; this process enables energy storage at high volumetric energy density. Among the electro-fuels options, FT (Fischer-Tropsch) fuel is attractive for heavy-duty trucks and non-road transportation applications. This study conducts a techno-economic analysis of FT liquid fuel production from H 2 and CO 2 using a detailed performance analysis. Minimum fuel selling price is estimated for a broad range of H 2 and CO 2 prices and for a range of potential CO 2 credits. The analysis indicates that H 2 price has the largest impact on the minimum selling price of FT fuel. FT fuel production with a CO 2 price of $17.3/metric ton requires an H 2 price of $0.8/kg to be cost-competitive with the pre-tax petroleum diesel price of $3.1/gal in 2050 (before the application of any CO 2 credits). When the H 2 price is $2.0/kg from central water electrolysis (2020 target), the minimum selling price of the FT fuel is $5.4–5.9/gal. A sensitivity analysis shows that future system optimization of FT fuel production could focus on improving the H 2 and CO 2 recycle contributions and FT fuel conversion ratio. The analysis results can be combined with various upstream systems for H 2 and CO 2 production.

08 HYDROGEN↗
DOE OSTI2024

Techno-economic and life cycle analysis of synthetic natural gas production from low-carbon H 2 and point-source or atmospheric CO 2 in the United States

Synthetic natural gas (SNG) is of great interest in reducing fossil energy consumption while maintaining compatibility with existing NG infrastructure and end-use applications equipment. SNG can be produced using clean H 2 generated from renewable or nuclear energy and CO 2 captured from stationary sources or the atmosphere. In this study, we develop an engineering process model of SNG production using Aspen Plus® and production scales reported by the industry. We examine the levelized cost and life cycle greenhouse gas (GHG) emissions of SNG production under various CO 2 supply scenarios. Considering the higher cost of H 2 transportation compared with CO 2 transportation, we assume that CO 2 feedstock is transported via pipeline to the H 2 production location, which is collocated with the SNG plant. We also evaluate the cost of CO 2 captured from the atmosphere, assuming the direct air capture process can occur near the SNG facility. Depending on the CO 2 supply chain, the levelized cost of SNG is estimated to be in the range of $\$45–76$ per million British thermal units (MMBtu) on a higher heating value (HHV) basis. The SNG production cost may be reduced to $\$27–57$/MMBtu-HHV by applying a tax credit available in the United States for low-carbon H 2 production (45V). With a lower electricity price of 3¢/kWh for water electrolysis and accounting for a 45V tax credit, the SNG cost reaches parity with the cost of fossil NG. Depending on the CO 2 supply chain, SNG can reduce life cycle GHG emissions by 52–88% compared with fossil NG.

03 NATURAL GAS↗
DOE OSTI2020

Voltammetry measurements in lithium chloride-lithium oxide (LiCl–Li 2 O) salt: An evaluation of working electrode materials

Instrumentation to provide process monitoring (PM) and safeguards for the oxide reduction (OR) step in the electrochemical processing of used oxide nuclear fuel is necessary to ensure equipment is operated as declared. Cyclic voltammetry (CV) has been proposed for real-time monitoring of the operation of an OR process for safeguards purposes. In this study, different materials including 316 stainless steel (SS), tantalum (Ta), molybdenum (Mo), tungsten (W), platinum (Pt), and iridium (Ir) were evaluated as potential working electrode (WE) materials based on their chemical inertness, corrosion resistance, and sensitivity in detecting Li 2 O and other chloride salts in the OR electrolyte. Of the electrodes evaluated, 316 SS, Ir, and Pt all performed reasonably well in the LiCl-Li 2 O electrolyte. Here, stainless steel was operated in the cathodic potential and had reasonable corrosion resistance and is relatively inexpensive. Iridium could be operated in both the cathodic and anodic potentials and was the most corrosion resistant of those evaluated. Platinum is limited to the anodic potential range, had reasonable corrosion resistance, and was the most sensitive to Li 2 O concentrations in the salt. In the development of a stand-alone safeguards instrumentation, our recommendation is a CV sensor fitted with both Ir and Pt WEs. The results in this study may also be helpful for anode material selection in other electrometallurgy industries, such as molten salt electrolysis.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗
DOE OSTI2023

Electrolyzer energy dominates separation costs in state-of-the-art CO 2 electrolyzers: Implications for single-pass CO 2 utilization

In low-temperature CO 2 electrolysis, a fundamental trade-off exists between maximizing electrolyzer performance and minimizing downstream CO 2 recovery. Here, by coupling a down-the-gas-channel electrolyzer model with a techno-economic analysis, we find that the optimal single-pass CO 2 conversion for ethylene production is typically low—on the order of 5%–10%—although larger optima are found if the H 2 faradic efficiency is very low. Similarly, strategies for eliminating carbonate crossover require more energy than downstream gas separation if they increase the cell potential by ~0.2 V; however, when CAPEX are accounted for, this “break-even” voltage increases to ~ 0.4 to 0.8 V for electricity prices varying from 6c/kWh to 1.5c/kWh. These findings are a consequence of the low energy requirements of industrial gas separation relative to electrochemical CO 2 reduction. Under most circumstances, maintaining near-optimal electrolyzer performance is more important than reducing or eliminating downstream gas separations.

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

Conformal high-entropy oxide coatings enable fast and durable surface oxygen reactions

Developing active and durable air electrodes for efficient oxygen reactions is challenging for protonic ceramic cells (PCCs), especially at temperatures below 550°C. Here, in this study, we report a rationally designed conformal coating with a high-entropy PrNi 0.2 Mn 0.2 Co 0.2 Fe 0.2 Cu 0.2 O 3−δ (PNMCFC) perovskite structure on the surface of a state-of-the-art PrBaCo 2 O 5+δ (PBC) air electrode. The formed hybrid air electrode (PNMCFC-PBC) shows faster surface oxygen kinetics and a more stable phase structure in high-humidity air than the bare PBC electrode. Further density functional theory calculations suggest that the conformal coating mitigates Ba segregation at the interface and improves oxygen-related reactions, enhancing overall stability and electrocatalytic performance. The cells with the developed hybrid electrodes show encouraging electrochemical performance at 550°C: a polarization resistance of 0.72 Ω cm 2 , a peak power density of 1.30 W cm −2 , an electrolysis current density of −1.36 A cm −2 at 1.3 V, and reasonable operating stabilities (∼200 h at 550°C).

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2020

Roll-to-roll production of catalyst coated membranes for low-temperature electrolyzers

Here we demonstrate a roll-to-roll (R2R) process for direct coating of anode catalyst layers on a polymer electrolyte membrane for low-temperature water electrolysis. To develop this process, we studied catalyst ink formulation, ink-membrane interactions, and coating quality. The catalyst inks were a mixture of iridium oxide (IrO2) and Nafion in a water and alcohol dispersion medium. The type of alcohol (methanol, ethanol, propanols) and water-to-alcohol ratio were varied to determine their influence on membrane swelling, dispersion quality, and coatability. Interactions of the ink dispersion medium with the membrane were characterized using sessile-drop contact-angle measurements. These measurements show that the ratio of water to alcohol has a strong influence on how rapidly the dispersion media is absorbed by the membrane. Rheology of the catalyst inks was measured to understand the microstructure of the catalyst particles in the ink. This analysis found that 1-propanol leads to better dispersion of the IrO2 particles than ethanol. Small-scale coating samples were prepared to understand coating uniformity and formation of irregularities. Subsequently, two water/1-propanol ratios (90:10 and 75:25) were down-selected for large-scale R2R slot die coating. The R2R catalyst-coated membrane (CCM) coating process increased catalyst layer production throughput by over 500x compared to our standard lab-scale spray coating. The CCMs obtained from this process were tested as single-cell membrane electrode assemblies. They exhibited a cell voltage of 1.91 V at a current density of 2 A/cm2, which is comparable to spray-coated CCMs. In conclusion, the work presented here demonstrates a continuous, scalable manufacturing process that eliminates the need for the decal transfer step typically used in CCM production.

42 ENGINEERING↗
DOE OSTI2024

Mitigation and Diagnosis of Pin-Hole Formation in Polymer Electrolyte Membrane Fuel Cells

In this work, we implement a calendering technique to flatten stray fibers within the gas diffusion media, thereby mitigating pin-hole formation in the hot-pressed MEAs. We have investigated the influence of calendering on the long-term durability for several types of gas diffusion electrodes (GDEs) using a combined chemical and mechanical accelerated stress test (AST). The calendered MEAs demonstrate an average AST lifetime improvement of 77% relative to the as-fabricated MEAs.

AMR↗
DOE OSTI2024

Effect of stoichiometry and hydration level on water domain size and transport in poly(aryl piperidinium) alkaline anion-exchange membranes

Alkaline water electrolysis holds promise in decarbonizing the global economy by enabling renewable hydrogen production with non-precious group metal catalysts. Anion exchange membranes are an important component of alkaline water electrolyzers and would ideally be durable while allowing for high hydroxide conductivity. The poly(aryl piperidinium) (PAP) class of polymers has attracted recent interest due to their good mechanical robustness and high ionic conductivity. Here, in this work, we perform atomistic molecular dynamics (MD) simulations of several PAP polymers at experimentally relevant hydration levels and polymer ion exchange capacities (IECs) to gain nanoscale insight into their properties and to help elucidate the trade-offs that result from tuning the IECs through the polymer stoichiometry. Our MD-predicted macroscopic polymer properties were found to be in good agreement with experimentally available polymer swelling ratios, water-occupied volumes, X-ray scattering, and ionic conductivities. The models show that for hydration levels greater than 8H 2 O per cation a single water cluster will form that percolates through the system. The growth in water cluster size results in large polymer swelling, the creation of larger channels with widths of 7 Å or larger, and nanophase separation between the hydrophilic domains and the polymer with characteristic length scales of approximately 20–30 Å. The experimentally observed lack of a strong X-ray scattering peak at low wavevectors can be explained by a cancellation between the polymer-polymer/water-water and polymer-water correlations and not a loss in nanophase separation. The overlap in coordination environments of the hydroxide oxygen and polymer nitrogen atoms implies that vehicular diffusion between cationic groups could play a role in hydroxide transport. The polymers' hydroxide and water diffusion constants increase by approximately an order of magnitude between hydration levels of 8 and 20H 2 O per cation. However, there are diminishing returns in hydroxide diffusion constant once the IEC exceeds 2.4 meq/g.

08 HYDROGEN↗
DOE OSTI2024

An electrochemical generator for the continual supply of 213 Bi from 225 Ac for use in targeted alpha therapy applications

Bismuth-213 is a radionuclide of interest for targeted alpha therapy and is supplied via a radiochemical generator system through the decay of 225 Ac. Radionuclide generators employ longer lived “parent” radionuclides to routinely supply shorter-lived “daughter” radionuclides. The traditional 225 Ac/ 213 Bi radiochemical generator relies on an organic cation exchange resin where 225 Ac binds to the resin and 213 Bi is routinely eluted. These resins degrade when they absorb large doses of ionizing radiation (>1 × 10 6 Gy/mg), which has been observed when the loading activity of 225 Ac exceeds 2.59*10 9 Bq (70 mCi). Herein we report the development of an electrochemical generator for the supply of 213Bi that has the potential to overcome this limitation. Bismuth-213 spontaneously electrodeposits onto nickel foils in 0.1 M hydrochloric acid at 70 °C. Using this method, we were able to plate an average of 73 ± 4 % of the 213 Bi in solution and obtain a final 213 Bi recovery of 65 ± 8 % in 0.1 M citrate pH 4.5 via reverse electrolysis using titanium as the cathode. The recovered 213Bi had an average radiochemical purity of >99.8 % and was successfully used to radiolabel DOTATATE with an average radiochemical yield of 85.1 % (not optimized).

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

Renewable biohydrogen production from lignocellulosic biomass using fermentation and integration of systems with other energy generation technologies

Biohydrogen is a clean and renewable source of energy. It can be produced by using technologies such as thermochemical, electrolysis, photoelectrochemical and biological, etc. Among these technologies, the biological method (dark fermentation) is considered more sustainable and ecofriendly. Dark fermentation involves anaerobic microbes which degrade carbohydrate rich substrate and produce hydrogen. Lignocellulosic biomass is an abundantly available raw material and can be utilized as an economic and renewable substrate for biohydrogen production. Although there are many hurdles, continuous advancements in lignocellulosic biomass pretreatment technology, microbial fermentation (mixed substrate and co-culture fermentation), the involvement of molecular biology techniques, and understanding of various factors (pH, T, addition of nanomaterials) effect on biohydrogen productivity and yield render this technology efficient and capable to meet future energy demands. Further integration of biohydrogen production technology with other products such as bio-alcohol, volatile fatty acids (VFAs), and methane have the potential to improve the efficiency and economics of the overall process. In this study, various methods used for lignocellulosic biomass pretreatment, technologies in trends to produce and improve biohydrogen production, a coproduction of other energy resources, and techno-economic analysis of biohydrogen production from lignocellulosic biomass are reviewed.

09 BIOMASS FUELS↗
DOE OSTI2021

Effect of electrode rinse solutions on the electrodialysis of concentrated salts

The data presented indicate that modest attention to the chemistry of the electrode rinse solution can yield as much as 56% improvement in process efficiency. When operating electrodialysis (ED) with salt concentrations greater than 10,000 mg/l (as NaCl) the amperage can be relatively high even at low voltages. To maximize the overall rate of ion transport from diluate to concentrate, there is a need to minimize resistances in the electrode cells since these can represent as much as 30% of the total resistances in the entire process and in this particular ED unit, represented resistance roughly equivalent to that within the membrane stack. This work describes the performance of a 10-cell pair, 200 cm 2 (0.02 m 2 ) per membrane, pilot ED unit operated in batch mode at 5 V potential. The feedstock to the stack was varied from 0.5% to 6% NaCl. Results from Volt-amp profiles (2.0–15 V) were used as the rationale for choosing the preferred electrode rinse solution, 90 g/l (kg/m 3 ) disodium sulfate at pH 12.5. The recommended solution of 30 g/l (kg/m 3 ) disodium sulfate at neutral pH was tested against stronger solutions (60, 90, and 120 g/l (kg/m 3 ) disodium sulfate) at neutral pH and with 1 g/l (kg/m 3 ) sodium hydroxide added to yield solutions at pH 12.5. There were stark differences in the performance of the ED unit between the solutions at pH 7 and those at pH 12.5. The slopes of the Volt-amp profiles improved indicating less resistance to ion flow at pH 12.5. Most of the difference can be attributed to the greater conductivity of sodium hydroxide compared to disodium sulfate, where even a modest addition of 1 g/l (kg/m 3 ) sodium hydroxide increased the conductivity of the solution between 8 and 20% depending on the concentration of disodium sulfate. Most notably, the initiation voltage was 2.39 ± 0.08 V with solutions at pH 7 and 1.99 V ± 0.04 V when the rinse solutions were around pH 12.5, a difference of around 0.42 V. Since the full batch runs were performed at 5.0 V, this 0.42 V differential represented a loss of 8% in process efficiency. A series of tests showed a shift in initiation voltage occurred between pH 11.5 and 12.5. Nernst equations for water electrolysis are coupled with a simple flux model that estimates the concentration of hydroxide and hydronium ions at the electrode surfaces. This model indicates that the potential demanded by the electrodes is directly linked to the current. Furthermore, there is a steep drop in the potential demanded by the anode when there is sufficient hydroxide available to generate oxygen from hydroxide as opposed to generation from water. The voltage demand is minimal at pH 12.5 and reflective of the reference standard voltage (just over 1.23 V predicted at 0.1 amps). However, the flux model predicts that the voltage demanded by the electrodes at pH 7 is 1.61 V at 0.1 amps (the lowest amperage measurable with the power pack). In conclusion, comparing this result to the reference standard (E 0 = -1.23 V) yields a satisfactory explanation for the observed difference below reference standard of 0.42 V.

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

Demonstration of an All-Refractory Corrosion-Resistant Molten Salt Pumping and Storage Infrastructure Up to 950 degrees C

Concentrating solar power (CSP) with thermal energy storage (TES) has an estimated cost similar to solar photovoltaics (PV) with lithium-ion batteries (LIB), but CSP + TES has the potential for significantly reduced cost by operating above 700 degrees C. However, this requires a TES medium and containment infrastructure which are chemically compatible and do not degrade above 700 degrees C. MgCl2-KCl-NaCl (MKN) salt is a promising medium, but when MKN salt has small amounts of water and oxygen dissolved in it, it excessively corrodes conventional commercial alloys. Here, we consider refractory materials including graphite, carbon-carbon composite (C/C), and molybdenum because they maintain high mechanical strength at elevated temperatures and are expected to resist corrosion by MKN salt. While selection of refractory materials is often constrained by the need to remain chemically stable in air, this work uses an enclosure filled with inert gas to allow the use of materials like graphite and molybdenum. Notably, graphite components can seal against liquids unlike many brittle refractory materials. We demonstrate a centrifugal pump and mechanical seals made of refractory materials in a laboratory-scale circulation loop, which successfully operated continuously for more than 49 h at temperatures ranging from 750 degrees C to 950 degrees C with no mechanical failures or chemical degradation of the refractory materials. To the best of our knowledge, this is the highest temperature molten salt circulation loop that has been successfully developed, and this refractory infrastructure allows for operation at even much higher temperatures (<1600 degrees C) if a storage medium with a lower vapor pressure is used. The principles of this architecture are relevant to other applications with high temperature flowing metals and salts including Generation IV nuclear fission reactors for power production and molten salt electrolysis reactors for metallurgical processing.

14 SOLAR ENERGY↗
DOE OSTI2025

Pulsed contact glow discharge electrification for online material quantification

Real-time elemental analysis of liquids in extreme environments remains a significant challenge for sensor development, particularly in applications such as advanced nuclear reactors. Plasma-based optical emission spectroscopy offers a promising solution. In this study, we investigate pulsed contact glow discharge electrolysis (CGDE) as an alternative plasma generation method for emission-based material quantification. Using aqueous NaCl solutions, we examine the role of discharge polarity on plasma behavior, emission characteristics, and spectral output. Our results demonstrate that cathodic discharges generate more energetic plasmas, enabling the detection of ionic species such as cerium, while anodic discharges favor atomic emission. These findings reveal a potential dual-mode sensing capability controlled by circuit configuration rather than hardware changes. Through synchronized measurements of emission, current, bubble, and spectral dynamics, we present a model in which electron emission and ohmic heating drive plasma formation. This model enhances our understanding of pulsed-CGDE and supports its potential as a versatile, adaptable platform for future deployment in high-temperature liquids such as molten salts.

98 - NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL↗
DOE OSTI2021

Removal of As(III) by Electrically Conducting Ultrafiltration Membranes

As(III) species are the predominant form of arsenic found in groundwater. However, nanofiltration (NF) and reverse osmosis (RO) membranes are often unable to effectively reject As(III). In this study, we fabricate highly conducting ultrafiltration (UF) membranes for effective As(III) rejection. Here, these membranes consist of a hydrophilic nickel-carbon nanotubes layer deposited on a UF support, and used as cathodes. Applying cathodic potentials significantly increased As(III) rejection in synthetic/real tap water, a result of locally elevated pH that is brought upon through water electrolysis at the membrane/water interface. The elevated pH conditions convert H 3 ASO 3 to H 2 AsO 3 – /HAsO 3 2– that are rejected by the negatively charged membranes. In addition, it was found that Mg(OH) 2 that precipitates on the membrane can further trap arsenic. Importantly, almost all As(III) passing through the membranes is oxidized to As(V) by hydrogen peroxide produced on the cathode, which significantly decreased its overall toxicity and mobility. Although the high pH along the membrane surface led to mineral scaling, this scale could be partially removed by backwashing the membrane. To the best of our knowledge, this is the first report of effective As(III) removal using low-pressure membranes, with As(III) rejection higher than that achieved by NF and RO, and high water permeance.

42 ENGINEERING↗
DOE OSTI2021

Bipolar Membranes for Ion Management in (Photo)Electrochemical Energy Conversion

Conspectus (Photo)electrochemical energy conversion is important in the development of a carbon-neutral energy economy because it can provide a pathway for mitigating the intermittency of renewable energy sources such as wind and solar. In order to operate efficiently, these technologies, which include photoelectrochemical cells, water and CO 2 electrolyzers, fuel cells, and redox flow batteries, require fast charge transfer kinetics at the electrode/electrolyte interface as well as robust ion management in the electrolyte. In conventional electrolyzers and fuel cells, the electrolyte is strongly acidic or basic and ionic current is carried by H + or OH – ions. In contrast, photoelectrodes and electrocatalysts for water splitting are often studied in buffered solutions. The question of ion balance in these systems led us to analyze the polarization losses due to ion concentration gradients in cells that employed various buffer–membrane combinations. Continuously driving the buffer ions across an ionomer membrane not only lowers the buffer capacity of an aqueous electrolyte but also introduces pH gradients that result in significant energy losses. To address the problem, we and other groups have studied the use of reverse-biased bipolar membranes (BPMs) in (photo)electrolytic cells. BPMs consist of an anion exchange layer (AEL) laminated with a cation exchange layer (CEL) and are usually equipped with a catalytic layer in between to accelerate the water dissociation reaction. At the AEL/CEL interface, water dissociates into protons and hydroxide ions, which replenish those consumed at the cathode and anode. Compared to conventional water electrolyzers with proton/anion exchange membranes (PEM/AEM), BPM electrolyzers provide the unique advantage of continuously operating the cathode and anode under different pH conditions, which is desirable when the two electrode reactions have different pH requirements. BPMs also enable the use of buffered electrolytes at pH values that are optimized for electrode stability and product selectivity in applications such as CO 2 electrolysis. Product crossover losses and CO 2 pumping can be dramatically reduced in BPM-based CO 2 electrolyzers, relative to conventional alkaline membranes, by electrostatic repulsion (of anionic products) and electroosmotic drag (for neutral products). BPM-based gas fed CO 2 electrolyzers can achieve high current density, but they suffer from low Faradaic efficiency (FE) due to the acidic local environment of the CEL. This problem can be mitigated by adding an aqueous buffering layer or by creating a weak acid cation exchange film on the CEL face of the membrane. The use of BPMs in fuel cells and redox flow batteries offers some interesting advantages. Configurations with both reverse and forward bias have been studied, but forward bias has been favored due to material compatibility, reaction kinetics, and thermodynamic considerations. The net reaction at the AEL/CEL interface is the acid–base neutralization reaction, which has a high inherent reaction rate constant, but in the BPM is limited to a nanometric space-charge layer and requires efficient catalysis to achieve high current density. Understanding the mechanism of the acid–base neutralization and the opposite process, the water dissociation reaction, will be essential for improving the performance of forward-biased BPMs. In conclusion, this Account reviews our current understanding of the working mechanisms of BPMs and discusses how we can use them to effectively manage ions for various (photo)electrochemical applications.

Yan, Zhifei↗
DOE OSTI2023

Diamonds in the Rough: Direct Surface Enhanced Infrared Spectroscopic Evidence of Nitrogen Reduction on Boron-Doped Diamond Supported Metal Catalysts

In situ investigations of electrocatalytic processes of increasing societal interest such as the nitrogen reduction reaction (NRR) re-quire aggressive experimental conditions that are not readily compatible with surface sensitive techniques such as attenuated total reflection surface enhanced infrared absorption spectroscopy (ATR-SEIRAS). A method for performing ATR-SEIRAS studies at very negative potentials where conventional IR-active films delaminate, and fail is reported. The method relies on a thin film of very robust boron-doped diamond deposited on a micromachined Si wafer, which provides extended mid-IR transparency at long wavelengths. SEIRAS activity is achieved by electrodepositing gold nanoparticles onto the conductive BDD layer. The Au@BDD layers are shown to sustain prolonged periods of electrolysis at negative potentials with no degradation of the modifying layer. The efficacy of these substrates for electrocatalysis is demonstrated by studying the reduction of N 2 at -1.5 V vs Ag/AgCl in an aqueous-based electrolyte. So under these conditions, direct spectroscopic evidence of both NH 3 and hydrazine formed from the nitrogen reduction reaction (NRR) is provided.

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

The Use of Microelectrodes in Molten Salt Electrochemistry

Molten salts have attracted considerable interest as essential media for advanced high-temperature technologies, including molten salt reactors, thermal energy storage, high-temperature electrolysis, and pyrochemical processing. Their ability to remain stable in liquid form at elevated temperatures, combined with favorable thermophysical properties and wide electrochemical windows, makes them highly suitable for applications involving heat transfer, energy storage, and hightemperature electrochemical processing. However, despite these advantages, molten salts present challenges due to their chemically reactive nature at high-temperatures, especially in the presence of oxidizing impurities. Salt chemistry can fluctuate through interactions with impurities over time, or fuel burnup in the case of molten salt reactors, often leading to the dissolution of metal species. This dynamic environment not only results in complex redox behavior but also promotes corrosion, which is rarely uniform and frequently manifests as localized degradation driven by structural materials’ compositional differences, electrochemical imbalances, and microstructural susceptibilities.

Kim, Changkyu [University of Wisconsin-Madison, WI↗