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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 271 records · Page 15
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Hydrogen production in microbial electrolysis cells with biocathodes

Electroautotrophic microbes at biocathodes in microbial electrolysis cells (MECs) can catalyze the hydrogen evolution reaction with low energy demand, facilitating long-term stable performance through specific and renewable biocatalysts. However, MECs have not yet reached commercialization due to a lack of understanding of the optimal microbial strains and reactor configurations for achieving high performance. Here, we critically analyze the criteria for the inocula selection, with a focus on the effect of hydrogenase activity and microbe–electrode interactions. We also evaluate the impact of the reactor design and key parameters, such as membrane type, composition, and electrode surface area on internal resistance, mass transport, and pH imbalances within MECs. Furthermore, this analysis paves the way for advancements that could propel biocathode-assisted MECs toward scalable hydrogen gas production.

Biotechnology & Applied Microbiology↗
DOE OSTI2026

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.

Flow path↗
DOE OSTI2022

Exploring Electrosynthesis: Bulk Electrolysis and Cyclic Voltammetry Analysis of the Shono Oxidation

As electrochemistry continues to gain broader acceptance and use within the organic chemistry community, it is important that advanced undergraduate students are exposed to fundamental and practical knowledge of electrochemical applications for chemical synthesis. Herein, we describe the development of an undergraduate laboratory experience that introduces synthetic and analytical electrochemistry concepts to an advanced organic chemistry class. Experiments focus on the electrooxidative α-functionalization of carbamates, more generally known as the Shono oxidation, and include cyclic voltammetry analysis of two cyclic carbamates and a constant current bulk electrolysis reaction. Here, the exercise offers students an authentic experience in organic electrochemistry, lays a practical and theoretical foundation for future engagement with concepts in electrochemistry and redox chemistry, and strengthens fundamental organic chemistry skills.

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

Nanobubble Formation and Coverage during High Current Density Alkaline Water Electrolysis

Gas bubbles are a necessary byproduct of water electrolysis whereby hydrogen and oxygen are produced from water. These attached gases reduce the electrode’s active area, which necessitates a deep understanding of the bubble life cycle starting from nanobubbles. Synchronized with the electrochemistry, the time evolution of the surface nanobubble size and coverage is resolved using grazing incidence small-angle X-ray scattering (GISAXS) and correlated with optical microscopy and theoretical calculations to show that a significant portion of the surface is covered in nanobubbles after larger micron-sized bubbles are observed. Further, these nanobubbles increase in number and decrease in size, toward 2 nm diameter, with the charge passed. The trend in size and number is consistent with an increase in supersaturation, which reduces the nascent bubble size. Altogether, this study suggests a significant portion of the surface contains nanobubbles and that strategies to reduce the dissolved hydrogen would be effective at reducing the nanobubble surface coverage.

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

Advancing the Performance of Anion Exchange Membrane Electrolysis by Employing a Powder-Based Ionomer during Anode Catalyst Layer Fabrication

The performance of anion exchange membrane water electrolysis (AEMWE) can be significantly improved by utilizing powdered ionomers during the fabrication of the anode catalyst layer (CL) to modify the CL properties. When comparing powdered ionomers to dispersed ionomers across various catalysts including cobalt oxide (Co 3 O 4 ), nickel−iron oxide (NiFe 2 O 4 ), and iridium oxide (IrO 2 ) the anode fabricated with powdered ionomers demonstrates improved performance in polarization curves, enhanced charge transfer kinetics, and reduced ohmic and transport losses, as evidenced by voltage breakdown and electrochemical impedance spectroscopy analyses. Optimal performance is achieved using a Co 3 O 4 catalyst with a 10 wt % powdered ionomer via the catalystcoated substrate method. Microscopy analyses reveal that electrodes formed with powdered ionomers during fabrication exhibit a more uniform catalyst and ionomer distribution, increased porosity with smaller pore areas, improved electronic conduction with less catalyst agglomeration isolated by a nonconductive ionomer, and enhanced interfacial contact with the membrane and transport layer. These findings highlight that ionomers in a powdered form can promote beneficial properties and are a promising approach to improving AEMWE efficiency.

08 HYDROGEN↗
DOE OSTI2020

Deconvolution of Water-Splitting on the Triple-Conducting Ruddlesden–Popper-Phase Anode for Protonic Ceramic Electrolysis Cells

Triple-conducting materials have been proved to improve the performance of popular protonic ceramic electrolysis cells. However, partially because of the complexity of the water splitting reaction involving three charge carriers, that is, oxygen (O 2– ), proton (H + ), and electron (e – ), the triple-conducting reaction mechanism was not clear, and the reaction conducting pathways have seldom been addressed. In this study, the triple conducting Ruddlesden–Popper phase Pr 1.75 Ba 0.25 NiO 4+δ as an anode on the BaCe 0.7 Zr 0.1 Y 0.1 Yb 0.1 O 3–δ electrolyte was fabricated and its electroresponses were characterized by electrochemical impedance spectroscopy with various atmospheres and temperatures. The impedance spectra are deconvoluted by means of the distribution of the relaxation time method. The surface exchange rate and chemical diffusivity of H + and O 2– are characterized by electrical conductivity relaxation. The physical locations of electrochemical processes are also identified by atomic layer deposition with a surface inhibitor. A microkinetics model is proposed toward conductivities, triple-conducting pathways, reactant dependency, surface exchange and bulk diffusion capabilities, and other relevant properties. Lastly, the rate-limiting steps and suggestions for further improvement of electrode performance are presented.

25 ENERGY STORAGE↗
DOE OSTI2026

Designing the Platinum Catalyst Layer for Improved Performance and Durability in Anion Exchange Membrane Water Electrolysis

To lower the cost of hydrogen produced by anion exchange membrane water electrolysis (AEMWE), it is critical to reduce the use of platinum group metal (PGM) catalysts within the device. While iridium has been successfully replaced with PGM-free catalysts at the anode, platinum-based (Pt) cathode catalysts are still required to meet the activity and durability targets. This study investigates the impact of commercial Pt/C catalyst loading, ionomer type and content, and electrode fabrication method on the cathode catalyst layer properties and AEMWE performance with the aim of determining the feasibility of reduced Pt loadings. While increased Pt loading is found to improve beginning-of-life performance, the effects are minimal above 0.6 mg/cm 2 . Ink characterization shows that ionomer type and content affect the ink stability, particle size, and percent of unbound ionomer, which further impact the homogeneity of the sprayed catalyst layers. The 5% PiperION cathode exhibited the highest performance, which may be attributed to a balance between the small particle size and the low proportion of unbound ionomer, minimizing kinetic and transport losses. Theoretical calculations show that the ionomers interact differently with the Pt surface, causing different surface charges and water adsorption strength and activating different mechanisms for hydrogen evolution. Pt-PiperION lowered the enthalpy of water-splitting by 0.1 eV compared to Pt alone and allowed for equal site access between adsorbed H* and OH* (both adsorbed at circa −2.2 eV). Although catalyst-coated membrane (CCM) fabrication techniques are desirable for scale-up, no performance enhancement is observed compared with the catalyst-coated substrate approach. Durability, as measured by degradation rates, Pt loss, and catalyst layer restructuring, was found to improve with increased Pt loadings, higher ionomer content, and CCM architectures. These findings provide important insight into the significant role of the cathode in AEMWE and strategies for maintaining the performance with low Pt loading or PGM-free catalysts.

08 HYDROGEN↗
DOE OSTI2026

Proton Conducting Silicon Oxide Membranes as a Fluorine Free Alternative to Nafion for Low Temperature Water Electrolysis

Driven by environmental and health concerns related to per- and polyfluoroalkyl substances (PFAS), there has been growing interest in developing fluorine-free proton (H + ) exchange membrane (PEM) materials for fuel cells and water electrolyzers. In this study, we present a side-by-side comparison of the key transport properties of submicron thick, PFAS-free amorphous silicon dioxide (SiO 2 ) membranes to Nafion, a fluorinated polymer electrolyte membrane that represents the industry standard for PEM fuel cells and electrolyzers. Here, measurements of proton (H + ) conductivity (σ H + ), hydrogen (H 2 ) permeability (P H 2 ), and electrical resistivity (ρ e – ) were conducted using model thin films comprised of SiO 2 membranes deposited by atomic layer deposition (ALD). Although the H + conductivity of the SiO 2 membranes is 2–3 orders of magnitude lower than Nafion, the addition of phosphorus dopants (PO x ) improves H + conductivity such that the area specific membrane resistance of thin (<50 nm) PO x -doped SiO 2 membranes is more than an order of magnitude lower than Nafion-117. Importantly, the safe operation of such nanoscale membranes within a PEM electrolyzer is feasible thanks to the low H 2 permeability of dense SiO 2 -based membranes, which are predicted to limit H 2 crossover rates to acceptable levels for pressures up to ≈ 100 bar. As a proof-of-principle demonstration, a chip-scale water electrolyzer based on 100 nm thick PO x -SiO 2 membrane is shown to achieve a current density of 2 A cm –2 at a potential of 2.5 V. If this technology can be successfully scaled up, H + conducting oxide membranes offer an attractive PFAS-free alternative to Nafion for efficient and durable water electrolysis and fuel cell technologies.

Nafion↗
DOE OSTI2026

Enhancing Oxygen Evolution Reaction and Stability in Proton-Conducting Solid Oxide Electrolysis Cells (p-SOECs) via a Porous Gadolinium-Doped Ceria Interlayer

Proton-conducting solid oxide electrolysis cells (p-SOECs) offer a promising pathway for intermediate temperature (400-600 °C) hydrogen production. However, they still face critical challenges related to sluggish oxygen evolution reaction (OER) kinetics and low Faradaic efficiencies. Here, in this work, we demonstrate that introducing a thin (~0.8 µm) porous Gd 0.1 Ce 0.9 O 1.95 (GDC) interlayer between a BaCo 0.8 Zr 0.1 Zn 0.1 O 3-δ (BCZZ) oxygen electrode and electrolyte significantly enhances p-SOEC performance. The GDC interlayer reduces polarization resistance by 48% (0.54 to 0.28 O cm 2 ) and increases Faradaic efficiency from 63% to 81% at -0.8 A/cm 2 and 600 °C. GDC interlayer p-SOECs display elevated effective H 2 current densities compared to control p-SOECs and reach up to -1.22 A/cm 2 at 1.3 V. Mechanistic studies on the interactions between GDC and BCZZ reveal that GDC intrinsically promotes OER kinetics by significantly reducing the polarization activation energy (Ea p ), dropping from 1.45 to 1.22 eV for full p-SOECs and 0.98 to 0.76 eV for symmetric cells. This promotional effect is localized in the electrochemically active region near the electrolyte interface. Durability testing for over 1500 hours under 50% H 2 O conditions indicates that the GDC interlayer also improves long-term stability, with a degradation rate 53% lower than control p-SOECs. By pinpointing the interfacial region where GDC exerts its promotional effect, highlighting its role in enhancing OER kinetics, and establishing interlayer engineering as a powerful technique, this work provides a unified pathway to simultaneously improve p-SOEC activity, Faradaic efficiency, and durability.

08 - HYDROGEN↗
DOE OSTI2023

Pulsed-Potential Electrolysis Enhances Electrochemical C–N Coupling by Reorienting Interfacial Ions

The electrochemical processing of anthropogenic CO 2 is an emerging technology aimed at utilizing renewable energies to synthesize valuable chemicals. Recently, developments in broadening the scope of the CO 2 reduction reaction (CO 2 RR) by enabling heteroatom coupling have surged with a focus on C–N bond formation. Herein, we investigate the factors that govern the selectivity and activity in synthesizing urea from environmentally malignant chemical feedstocks (CO 2 and NO 3 – ). Through a combination of electrolyte optimization and pulsed potential electrolysis, electrochemical urea production was optimized to a Faradaic efficiency of 60.4% with current densities reaching as high as 310 μA cm –2 . This work was further supported by in situ surface enhanced infrared absorbance spectroscopy that reveals the formation of C–N-related species at low overpotentials. Density functional theory calculations revealed that the reaction progresses between early reduction intermediates for the CO 2 RR and NO 3 RR and offered insights into the impacts of pulsed-potential on substrate transport.

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

NH 3 -Mediated Reactive Capture and Conversion: Integrating CO 2 Absorption from Flue Gas with CO Production via NH 4 HCO 3 Electrolysis

Efficient carbon capture and utilization require strategies that minimize energy penalties of CO 2 regeneration and compression. Reactive capture and conversion (RCC) address this challenge by integrating capture with direct electrochemical conversion. Here, we show an NH3-mediated tandem RCC system that couples capture of CO 2 from simulated flue gas (10% v/v CO 2 in N 2 ) with electroreduction of NH 4 HCO 3 to CO over a Ni single-atom catalyst (Ni-SAC). Speciation modeling and capture experiments revealed that a deep CO 2 capture with C/N ratio of 0.65 was achieved using 2.5 M NH 3 from simulated flue gas. Electrolysis of the resulting NH 4 HCO 3 on the Ni- SAC delivered an 85% CO Faradaic efficiency at 100 mA/cm 2 with excellent tolerance to NH 3 /NH 4 + as confirmed by DFT calculations and ab initio molecular dynamics (AIMD) simulations. Further, the technoeconomic analysis established a levelized total cost of CO manufacturing of $25.43/kmol, gauging the practical viability. Overall, this study holds great potential to decarbonize the chemical manufacturing industry while reducing synthetic production costs.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2021

Comparative Techno-Economic and Life Cycle Analysis of Water Oxidation and Hydrogen Oxidation at the Anode in a CO 2 Electrolysis to Ethylene System

We compare the economic viability of employing hydrogen oxidation versus water oxidation at the anode of a commercial-scale electrolysis plant that converts CO 2 to ethylene. We vary the electrolyzer capital cost, membrane lifetime, and renewable electricity price to represent a current and future market scenario. We find that anodic hydrogen oxidation with membraneless reactor design can reduce the electrolyzer capital cost by up to 48% and reduce electricity demand by at least 50% with the current underdeveloped electrolyzer market. These capital and operating cost savings could further lead to a lower ethylene production cost from anodic hydrogen oxidation than the anodic water oxidation system with hydrogen supplied at less than $\$6$ kg. In the future scenario with a fully developed electrolyzer market and cheap renewable electricity, we find that the anodic hydrogen oxidation system requires hydrogen cheaper than $0.7/kg to compete with the anodic water oxidation system. Moreover, hydrogen oxidation at the anode enables extremely low cradle-to-gate emission ethylene by utilizing negative emission hydrogen such as biomass gasification with carbon capture and sequestration, ~240% lower than ethylene produced from the wind/solar electricity-driven water oxidation system. Furthermore, this low carbon footprint ethylene can further boost the economic competitiveness for anodic hydrogen oxidation with a future carbon credit market.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

eReaxFF force field development for BaZr 0.8 Y 0.2 O 3-δ solid oxide electrolysis cells applications

The use of solid-oxide materials in electrocatalysis applications, especially in hydrogen-evolution reactions, is promising. However, further improvements are warranted to overcome the fundamental bottlenecks to enhancing the performance of solid-oxide electrolysis cells (SOECs), which is directly linked to the more-refined fundamental understanding of complex physical and chemical phenomena and mass exchanges that take place at the surfaces and in the bulk of electrocatalysis materials. Here, we developed an eReaxFF force field for barium zirconate doped with 20 mol% of yttrium, BaZr 0.8 Y 0.2 O 3-δ (BZY20) to enable a systematic, large-length-scale, and longer-timescale atomistic simulation of solid-oxide electrocatalysis for hydrogen generation. All parameters for the eReaxFF were optimized to reproduce quantum-mechanical (QM) calculations on relevant condensed phase and cluster systems describing oxygen vacancies, vacancy migrations, electron localization, water adsorption, water splitting, and hydrogen generation on the surfaces of the BZY20 solid oxide. Using the developed force field, we performed both zero-voltage (excess electrons absent) and non-zero-voltage (excess electrons present) molecular dynamics simulations to observe water adsorption, water splitting, proton migration, oxygen-vacancy migrations, and eventual hydrogen-production reactions. Based on investigations offered in the present study, we conclude that the eReaxFF force field-based approach can enable computationally efficient simulations for electron conductivity, electron leakage, and other non-zero-voltage effects on the solid oxide materials using the explicit-electron concept. Moreover, we demonstrate how the eReaxFF force field-based atomistic-simulation approach can enhance our understanding of processes in SOEC applications and potentially other renewable-energy applications.

08 HYDROGEN↗
DOE OSTI2025

Conformally coated scaffold design using water-tolerant Pr 1.8 Ba 0.2 NiO 4.1 for protonic ceramic electrochemical cells with 5,000-h electrolysis stability

Protonic ceramic electrochemical cells (PCECs) have potential as long-duration energy storage systems. However, their operational stability is limited under industrially relevant conditions due to the intrinsic chemical instability of doped barium cerate-based electrolytes and oxygen electrodes against H 2 O, as well as the poor electrode–electrolyte interfacial contact. Here, in this study, we present a conformally coated scaffold (CCS) design to comprehensively address these issues. A porous proton-conducting scaffold is constructed and conformally coated with Pr 1.8 Ba 0.2 NiO 4.1 electrocatalyst, which has high chemical stability against H 2 O, triple conductivity and hydration capability, and protects vulnerable electrolytes from H 2 O. The CCS structure consolidates the electrode–electrolyte interfacial bonding to enable fast proton transfer in the percolated network. This design enables PCECs to reach electrolysis stability for 5,000 h at −1.5 A cm−2 and 600 °C in 40% H 2 O. This work provides a general strategy to stabilize PCECs and offers guidance for designing resilient and stable solid-state energy storage systems.

Protonic ceramic electrochemical cell↗
DOE OSTI2025

Decoupling electrode kinetics to elucidate reaction mechanisms in alkaline water electrolysis

Alkaline water electrolysis (AWE) presents key advantages, including reduced material costs, enhanced operational stability, and compatibility with non-precious metal catalysts, positioning it as a scalable route for hydrogen production. In this study, we introduce a minimally invasive single-cell configuration incorporating a reference electrode via diaphragm extension to form an internal ion channel. This setup, combined with an interfaced potentiostat and auxiliary electrometer, enables real-time, independent monitoring of anode and cathode behavior, offering high-resolution electrochemical diagnostics. While it is well established that the hydrogen evolution reaction (HER) exhibits sluggish kinetics in alkaline media, our study reveals that this limitation persists even in practical AWE systems where nickel-based substrates are used as electrodes. This observation is supported by both experimental data and voltage breakdown modeling. Arrhenius-type analysis reveals that localized electric fields induced by catalysts shift the reaction kinetics from classical Butler–Volmer behavior toward a Marcus-like regime, where interfacial molecular dynamics and bimolecular charge transfer dominate. We propose a semi-empirical model and a surficial reaction mechanism to describe these dynamics. This work underscores the critical need for cathode innovation and provides a rational framework for designing advanced catalysts and electrode architectures to optimize AWE performance.

08 HYDROGEN↗
DOE OSTI2025

Voltage breakdown analyses in anion exchange membrane water electrolysis – the contributions of catalyst layer resistance on overall overpotentials

Despite many recent advances, overpotentials remain high for anion exchange membrane water electrolyzers (AEMWEs). Voltage breakdown analyses (VBA) can help decouple the origins of overpotentials and facilitate design decisions to improve cell performance, but studies investigating how to adapt and apply VBA to AEMWEs are lacking. Specifically, catalyst layer resistances and their contributions to overpotentials are not consistently quantified in water electrolysis and are rarely quantified for AEMWEs. This work presents a systematic methodology for VBA tailored to AEMWEs, including an approach to Tafel analysis in the absence of a reference electrode and under conditions where both the oxygen evolution reaction and hydrogen evolution reaction exhibit significant overpotentials. Catalyst layer resistance contributions are diagnosed via changes in the catalyst layer thickness, transport layer porosity, ionomer content, and electrolyte concentration. In this study, we explain discrepancies between inherent catalytic kinetics and device level performance and identify catalyst layer design strategies to reduce catalyst layer resistances.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

A reaction mechanism for plasma electrolysis of AgNO 3 forming silver nanoclusters and nanoparticles

In plasma-driven solution electrolysis (PDSE), gas-phase plasma-produced species interact with an electrolytic solution to produce, for example, nanoparticles. An atmospheric pressure plasma jet (APPJ) directed onto a liquid solution containing a metallic salt will promote reduction of metallic ions in solution, generating metallic clusters that nucleate to form nanoparticles. In this article, results from a computational investigation are discussed of a PDSE process in which a radio-frequency APPJ sustained in helium impinges on a silver nitrate solution, resulting in growth of silver nanoparticles. A reaction mechanism was developed and implemented in a global plasma chemistry model to predict nanoparticle growth. To develop the reaction mechanism, density functional theory was used to generate probable silver growth pathways up to Ag 9 . Neutral clusters larger than Ag 9 were classified as nanoparticles. Kinetic reaction rate coefficients for thermodynamically favorable growth pathways were estimated based on an existing, empirically determined base reaction mechanism for smaller Ag particle interactions. These rates were used in conjunction with diffusion-controlled reaction rate coefficients that were calculated for other Ag species. The role of anions in reduction of Agn ions in forming nanoparticles is also discussed. Oxygen containing impurities or admixtures to the helium, air entrainment into the APPJ, and dissociation of saturated water vapor above the solution can produce additional reactive oxygen species in solution, resulting in the production of anions and O 2 – in particular. For a given molarity, delivering a sufficient fluence of reducing species will produce similar nanoparticle densities and sizes for all applied power levels. In conclusion, comparisons are made to alternate models for nanoparticle formation, including charged nanoparticles and use of direct current plasmas.

36 MATERIALS SCIENCE↗