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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 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

A Robust, Scalable Platform for the Electrochemical Conversion of CO 2 to Formate: Identifying Pathways to Higher Energy Efficiencies

This work demonstrated a robust, scalable cell architecture for electroreduction of CO 2 (CO 2 R). An up to 90% faradaic efficiency for the conversion of CO 2 R to formate at 500 mA/cm 2 was realized at a 25 cm2 gas diffusion electrode (GDE) with a carbon-supported SnO 2 electrocatalyst. Furthermore, a 1.27 mm thick catholyte was used between the bipolar membrane and cathode GDE, which could be further reduced to tens of micrometers upon refinement. The deconvolution of the potential drop from each individual component/process guides the pathways to higher energy efficiencies of CO 2 R at this platform. Significant changes in the agglomerate size and aspect ratio on the electrode before and after an 11 h test were revealed by nano-CT, suggesting reduced CO 2 accessibility from electrode degradation. The versatility of this CO 2 R testing platform enables the ability to assess materials, components, and interactions at scales more in line with future devices.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2024

Stable Pentagonal Layered Palladium Diselenide Enables Rapid Electrosynthesis of Hydrogen Peroxide

Electrosynthesis of hydrogen peroxide (H 2 O 2 ) via the two-electron oxygen reduction reaction (2e – ORR) is promising for various practical applications, such as wastewater treatment. However, few electrocatalysts are active and selective for 2e – ORR yet are also resistant to catalyst leaching under realistic operating conditions. Here, a joint experimental and computational study reveals active and stable 2e – ORR catalysis in neutral media over layered PdSe 2 with a unique pentagonal puckered ring structure type. Computations predict active and selective 2e – ORR on the basal plane and edge of PdSe 2 , but with distinct kinetic behaviors. Further, electrochemical measurements of hydrothermally synthesized PdSe 2 nanoplates show a higher 2e – ORR activity than other Pd–Se compounds (Pd 4 Se and Pd 17 Se 15 ). PdSe 2 on a gas diffusion electrode can rapidly accumulate H 2 O 2 in buffered neutral solution under a high current density. The electrochemical stability of PdSe 2 is further confirmed by long device operational stability, elemental analysis of the catalyst and electrolyte, and synchrotron X-ray absorption spectroscopy. This work establishes a new efficient and stable 2e – ORR catalyst at practical current densities and opens catalyst designs utilizing the unique layered pentagonal structure motif.

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

Molecular engineering of dispersed nickel phthalocyanines on carbon nanotubes for selective CO 2 reduction

Electrochemical reduction of CO 2 is a promising route for sustainable production of fuels. A grand challenge is developing low-cost and efficient electrocatalysts that can enable rapid conversion with high product selectivity. Here we design a series of nickel phthalocyanine molecules supported on carbon nanotubes as molecularly dispersed electrocatalysts (MDEs), achieving CO 2 reduction performances that are superior to aggregated molecular catalysts in terms of stability, activity and selectivity. The optimized MDE with methoxy group functionalization solves the stability issue of the original nickel phthalocyanine catalyst and catalyses the conversion of CO 2 to CO with >99.5% selectivity at high current densities of up to -300 mA cm -2 in a gas diffusion electrode device with stable operation at -150 mA cm -2 for 40 h. The well-defined active sites of MDEs also facilitate the in-depth mechanistic understandings from in situ/operando X-ray absorption spectroscopy and theoretical calculations on structural factors that affect electrocatalytic performance.

42 ENGINEERING↗
DOE OSTI2026

Low-frequency electrochemical pulsing to manage flooding and salt precipitation in zero-gap CO 2 -to-ethylene electrolyzers

The electrochemical reduction of carbon dioxide (CO 2 ) to ethylene presents a promising route for utilizing exhaust gases to produce value-added chemicals with broad manufacturing applications. While zero-gap electrolyzer architectures show great potential to enable commercial-scale CO 2 -to-ethylene conversion, their performance is often limited by failure within the first 100 hours. In this work, we demonstrate that a low-frequency electrochemical pulsing protocol effectively mitigates carbonate salt precipitation and flooding by managing water transport to and through the cathode gas diffusion electrode and associated flow fields. Operando neutron imaging further reveals the dynamics of water crossover and flooding, emphasizing the intricate interplay between electrochemical operation and ionic transport. By mitigating short-term flooding and salt precipitation failure modes, this study establishes a foundation for understanding long-term degradation mechanisms and advancing the practical viability of CO 2 electrolyzers for industrial-scale applications.

36 MATERIALS SCIENCE↗
DOE OSTI2026

In situ catalyst activation and regeneration enable energy-efficient high-current CO 2 reduction to ethanol-rich C 2+ mixtures

Electrochemical conversion of dissolved CO 2 in bicarbonate electrolytes, i.e., bicarbonate electrolysis, offers distinct advantages over gas diffusion electrode systems by enabling direct utilization of the CO 2 capture electrolyte while bypassing the energy-intensive CO 2 release step. However, bicarbonate electrolysis faces challenges such as CO 2 mass-transfer limitation, local pH-driven CO 2 depletion, and high cathodic potentials. The higher potential often causes catalyst surface reorganization, leading to a gradual loss of active sites and variations in selectivity during CO 2 reduction. Here, we report a directed, in situ activation and regeneration method that allows precatalysts to equilibrate under dynamic (pulsed) electrolysis conditions. We demonstrate in situ activation of a scalable Cu 2 O/Cu mesh that, under short-width (t = 4 s) pulsed electrolysis, provides stable mixed oxidation states of Cu, favoring the formation of an ethanol-rich crude mixture. The pulsed electrolysis waveform, consisting of six distinct segments, is tuned to form Cu + oxides, which are then reduced to generate local alkaline conditions favoring C–C coupling. This synergistic effect results in FEs of 73% for C2+ products and 39% for ethanol at an applied current density of −150 mA cm −2 and a cathodic potential of −1.45 V (vs. RHE). The overall half-cell energy efficiency is ∼30% for C 2+ products. The in situ Raman experiments confirm the role of pCO 2 R in dynamically regenerating Cu+-containing surface species during pulsed operation, thereby steering selectivity towards C 2+ products. A comprehensive multiscale, multiphysics model is developed to investigate the dynamic behavior of copper surface species (Cu, Cu + , and Cu 2+ ) and local microenvironmental conditions during the pCO 2 R. The results reveal that the coexistence of different copper oxidation states, especially the Cu+ intermediate, is critical in steering selectivity towards multicarbon (C 2+ ) products. The dynamic modulation of surface redox states via tailored pulsing strategies favors C–C coupling pathways by inducing localized alkaline conditions and stabilizing reactive intermediates. This work establishes a predictive modeling platform that links pulse waveform design with mechanistic insights into catalyst state evolution and product selectivity. Overall, this study provides valuable insights into the synergistic effect of in situ activation of pre-catalysts and pulsed electrolysis for higher selectivity towards C 2+ products.

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

Oxygen Reduction Reaction Activity of Nanocolumnar Platinum Thin Films by High Pressure Sputtering

Nanocolumnar platinum thin films (Pt-TFs) were produced by high pressure sputtering (HIPS) and investigated as oxygen reduction reaction electrocatalysts for polymer electrolyte membrane fuel cells. Conventional high-density Pt-TF prepared by low pressure sputtering was also studied for comparison. Pt-TFs were deposited on a microporous layer (MPL)-like surface composed of carbon particles to mimic catalyst-coated gas diffusion electrodes. Electron microscopy imaging revealed that HIPS Pt-TFs developed a cauliflower-like columnar microstructure, which originated from a shadowing effect during HIPS. This shadowing effect is enhanced on the rough surface of the MPL-like carbon that leads to the nano-cauliflower formation. With this approach, we also aimed to relate the catalyst performance obtained by benchtop tests directly to membrane electrode assembly test results. The electrochemically active surface area of Pt-TFs increased from 10 to 19 m 2 /g with increasing sputter pressure. Specific activity of conventional high-density and nanocolumnar films were similar at ~600 μA/cm 2 , which is likely due to their similar crystal grain sizes, >5 nm. On the other hand, mass-specific (MA) activity values increased from ~0.06 A/mgPt for conventional Pt-TF to ~0.13 A/mgPt for HIPS Pt-TFs, which is consistent with the columnar microstructure of HIPS films providing a better catalyst utilization compared to conventional Pt-TF.

08 HYDROGEN↗
DOE OSTI2020

Microstructural Evolution and ORR Activity of Nanocolumnar Platinum Thin Films with Different Mass Loadings Grown by High Pressure Sputtering

Nanocolumnar platinum thin films (Pt-TFs) with different Pt mass loadings were grown by high pressure sputtering (HIPS) and investigated as oxygen reduction reaction (ORR) electrocatalysts for polymer electrolyte membrane fuel cell applications. Mass loading was controlled by changing the sputter deposition time. A cauliflower-like columnar microstructure was achieved by depositing the Pt-TFs onto a microporous layer (MPL)-like surface composed of carbon particles in order to mimic catalyst-coated gas diffusion electrodes. Microstructural evolution of HIPS Pt-TFs and their ORR activity were investigated. Electrochemical characterization of the nanocolumnar Pt-TFs was performed by cyclic voltammetry and rotating disk electrode measurements on Pt-TF/MPL-like-layer/glassy-carbon samples in an aqueous perchloric acid electrolyte. The electrochemically active surface area increased from 18 to 39 m 2 g –1 as the Pt mass loading was decreased. Specific activity of the films was similar (~600 μA cm –2 ) for all Pt mass loadings, due to the similar nanoparticle sizes of ~5 nm as observed by transmission electron microscopy and X-ray diffraction. Furthermore, mass activity of the films increased from 0.11 to 0.26 A mg –1 as the Pt mass loading was decreased, which is an indication of the effective Pt utilization and better access through the catalyst layer at lower Pt mass loadings.

08 HYDROGEN↗
DOE OSTI2024

Electrifying Critical Mineral Refinement in the US (CRADA Final Report)

The technical founder of Aepnus Technology Inc. was competitively selected for support by Cyclotron Road, a U.S. Department of Energy (DOE) Lab-Embedded Entrepreneurship Program (LEEP) through an approved merit review process. Through this program, Aepnus Technology has collaborated with Lawrence Berkeley National Laboratory (LBNL) to develop and validate a novel electrolysis platform targeting the recycling of sodium sulfate waste, a pervasive byproduct in the battery supply chain. The platform aims to address inefficiencies in conventional electrolysis by leveraging Aepnus' proprietary gas diffusion electrode (GDE) technology, which replaces precious metal catalysts, such as iridium, to achieve high efficiency, reduced operational costs, and enhanced durability.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
NASA NTRS1980

Preparation and evaluation of advanced electrocatalysts for phosphoric acid fuel cells

Results are presented for hydrogen oxidation and hydrogen oxidation poisoned by carbon monoxide at levels between 0 and 30%. Due to the high activities that are now being observed for our platinum based electrocatalysts, the hydrogen concentrations were reduced to 10% levels in the gas supplies. Perturbation techniques were used to determine that a mechanism for the efficient operation of our porous gas diffusion electrodes is diffusion of the carbon monoxide out of the electrode structure through the electrolyte film on the electro-catalyst. A survey of the literature on platinum group materials (PGM) was carried out so that an identification of successful electrocatalysts could be made. Two PGM electrocatalysts were prepared and performance data for hydrogen oxidation in hot phosphoric acid in the presence of high carbon monoxide concentrations showed that they matched the best platinum on carbon electrocatalysts but with an electrocatalyst cost that was half of the platinum catalyst cost.

Stonehart, P.↗
NASA NTRS1990

Lead-ruthenium pyrochlores as oxygen electrocatalysts

An investigation of lead-ruthenium pyrochlores of the structure Pb2(Ru/2-x/Pb/x/) O7-y for use as oxygen electrocatalysts in alkaline media is discussed. Lead-ruthenium pyrochlore mixed metal oxides were prepared and characterized by X-ray diffraction, BET surface area, dry powder conductivity, and chemical stability. Gas diffusion electrodes were developed specifically for the lead-ruthenium pyrochlore materials. Also investigated were the effects of varying electrode fabrication parameters on the oxygen reduction performance of the lead-ruthenium pyrochlore electrocatalyst. Long-term stability performance was also evaluated. The oxygen reduction performance of the pyrochlore electrocatalyst is considerably higher than that of the state-of-the-art gold-platinum alloy electrocatalyst currently used by NASA. Furthermore, the pyrochlore electrocatalysts are attractive candidates for high-performance pressurized alkaline fuel cells.

Anderson, E. B.↗
NASA NTRS2010

Electrochemical Hydrogen Peroxide Generator

Two-electron reduction of oxygen to produce hydrogen peroxide is a much researched topic. Most of the work has been done in the production of hydrogen peroxide in basic media, in order to address the needs of the pulp and paper industry. However, peroxides under alkaline conditions show poor stabilities and are not useful in disinfection applications. There is a need to design electrocatalysts that are stable and provide good current and energy efficiencies to produce hydrogen peroxide under acidic conditions. The innovation focuses on the in situ generation of hydrogen peroxide using an electrochemical cell having a gas diffusion electrode as the cathode (electrode connected to the negative pole of the power supply) and a platinized titanium anode. The cathode and anode compartments are separated by a readily available cation-exchange membrane (Nafion 117). The anode compartment is fed with deionized water. Generation of oxygen is the anode reaction. Protons from the anode compartment are transferred across the cation-exchange membrane to the cathode compartment by electrostatic attraction towards the negatively charged electrode. The cathode compartment is fed with oxygen. Here, hydrogen peroxide is generated by the reduction of oxygen. Water may also be generated in the cathode. A small amount of water is also transported across the membrane along with hydrated protons transported across the membrane. Generally, each proton is hydrated with 3-5 molecules. The process is unique because hydrogen peroxide is formed as a high-purity aqueous solution. Since there are no hazardous chemicals or liquids used in the process, the disinfection product can be applied directly to water, before entering a water filtration unit to disinfect the incoming water and to prevent the build up of heterotrophic bacteria, for example, in carbon based filters. The competitive advantages of this process are: 1. No consumable chemicals are needed in the process. The only raw materials needed are water and oxygen or air. 2. The product is pure and can therefore be used in disinfection applications directly or after proper dilution with water. 3. Oxygen generated in the anode compartment is used in the electrochemical reduction process; in addition, external oxygen is used to establish a high flow rate in the cathode compartment to remove the desired product efficiently. Exiting oxygen can be recycled after separation of liquid hydrogen peroxide product, if so desired. 4. The process can be designed for peroxide generation under microgravity conditions. 5. High concentrations of the order of 6-7 wt% can be generated by this method. This method at the time of this reporting is superior to what other researchers have reported. 6. The cell design allows for stacking of cells to increase the hydrogen peroxide production. 7. The catalyst mix containing a diquaternary ammonium compound enabled not only higher concentration of hydrogen peroxide but also higher current efficiency, improved energy efficiency, and catalyst stability. 8. The activity of the catalyst is maintained even after repeated periods of system shutdown. 9. The catalyst system can be extended for fuel-cell cathodes with suitable modifications.

Tennakoon, Charles L. K.↗
NASA NTRSDate not supplied

Modeling Electrolytic O2 Recovery from Metabolic CO2 for Advanced Closed Loop Life Support Systems in Extraterrestrial Human Missions

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 human missions to the Moon and Mars will necessitate a sustainable and highly efficient metabolic oxygen recovery 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 metabolic O2 recovery efficiency, expand mission sustainability, and reduce complexity of the system. The novel design combines CO2 conversion to O2 along with C2H4 as byproduct and water electrolysis (currently conducted in two separate units) into a single compact unit that runs at standard conditions and is theoretically capable of generating O2 with a theoretical maximum metabolic CO2 conversion of 73% while consuming less than metabolic water. 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 electrical current density distributions is coupled in the model with all the other physics phenomena involved in the MFECR’s process, such as two-phase flow, free and porous fluid regimes, multicomponent mass transfer, heat transfer, and DC electrical current generation along with Joule heating effect. The EC reaction sections of the MFECR consists of two porous gas diffusion electrodes (GDE) and an electrolyte serpentine channel sandwiched in the middle. The CO2 feeds the cathode serpentine channel and part of the O2 product is fed back to the anode serpentine chamber. An alkaline solution feeds the electrolyte serpentine chamber wetting the GDEs of both, the anode and cathode allowing the OH- ionic transport between them. The EC reactions in the cathode’s GDE yield C2H4 from CO2 and H2 from water while the EC reaction in the anode’s GDE yields O2. The authors will present in this paper the validation of the model using experimental data and the utilization of the validated model in building a reliable simulator that will not only assist the authors on the MFECR design but also the optimization of its operation in the ISS and future spatial human missions.

Jesus A Dominguez↗
DOE OSTI2022

Microwatt fuel cell stack

A microwatt fuel cell stack that demonstrates a wide range temperature tolerance, low reactant cross-over and leakage, low internal leakage current, and/or effective water transport is disclosed. Both H 2 and O 2 may be supplied directly to the fuel cell stack (i.e., dead-ended). One-piece gas diffusion electrodes (GDEs) may serve as both the active electrode and manifold port. Water removal may be accomplished by permeation through the membrane to “fins” exposed by notches in the bipolar plates and gaskets.

Wilson, Mahlon Scott↗
DOE OSTI2023

Electrolyzers for the reduction of carbon dioxide to formate

The present disclosure relates to an electrochemical flow cell that includes a gap positioned between an ion exchange membrane (IEM) and a cathode gas diffusion electrode (GDE), where the gap is positioned to contain a liquid and the gap has a thickness value, as defined by the distance between the IEM and the cathode GDE, of between greater than zero mm and less than about 2.0 mm. In some embodiments of the present disclosure, the gap may be between about 0.1 mm and about 1.0 mm.

Klein, Jr., Walter Ellis↗
DOE OSTI2024

Continuous Flow Photoelectrochemical Reactor with Gas Permeable Photocathode: Enhanced Photocurrent and Partial Current Density for CO 2 Reduction

Photoelectrochemical (PEC) CO 2 reduction using a photocathode is an attractive method for making valuable chemical products due to its simplicity and lower overpotential requirements. However, previous PEC processes have often been diffusion-limited leading to low production rates of the CO 2 reduction reaction, due to inefficient gas diffusion through the liquid electrolyte to the catalyst surface, particularly at high current densities. In this study, a gas-permeable photocathode in a continuous flow PEC reactor is incorporated, which facilitates the direct supply of CO 2 gas to the photocathode-electrolyte interface, unlike dark reaction-based flow reactors. This concept is demonstrated using Ag-TiO 2 on carbon paper, illuminated through a quartz window and flowing liquid electrolyte. CO 2 supply is managed via pressure and flow control on the non-illuminated side of the carbon paper. The photocurrent density is significantly influenced by the flow rates and pressure of CO 2 gas, and the electrolyte flow rates. Compared to the traditional H-cell, the continuous PEC flow reactor achieves ≈10-fold increase in CO faradaic efficiency, 30-fold increase in production rate and 16-fold increase in stability without catalyst modifications. This work provides essential insights into the design and application of continuous gas-liquid flow PEC reactor systems, highlighting their potential for other PEC reactions.

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

Integrated Reference Electrodes in Anion-Exchange-Membrane Electrolyzers: Impact of Stainless-Steel Gas-Diffusion Layers and Internal Mechanical Pressure

Alkaline-membrane electrolyzers operating in pure water might provide scalable low-cost H 2 production but currently lag in performance and durability compared to commercial technologies. Typically, membrane–electrode assemblies (MEAs) are optimized in electrolyzers by changing one parameter at a time and assessing the resulting system performance via two-electrode polarization and impedance measurements. These approaches are limited in their ability to assign performance changes and durability to specific electrodes or processes. We integrate a reference electrode with the MEA to separate anode and cathode responses in both polarization and impedance measurements. Here we illustrate the power of the approach by showing how the fiber diameter of stainless-steel gas-diffusion layers (GDLs) affects performance solely at the anode, while changing the thickness of the cathode GDL simultaneously affects the performance of the anode and cathode due to changes in internal pressure from mechanical compression. This finding was obscured in conventional two-electrode measurements. The work thus guides both high-performance alkaline-membrane water-electrolyzer development and illustrates a useful strategy to study structure–activity relationships in the MEA.

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

Ultrathin platinum nanowire based electrodes for high-efficiency hydrogen generation in practical electrolyzer cells

Significant reduction of noble metal catalyst loading and simplification of electrode fabrication are urgently needed in order to lower the cost of proton exchange membrane electrolyzer cells (PEMECs) for large-scale hydrogen production. Herein, we report an integrated electrode design comprising in-situ grown platinum nanowires (PtNW) on ultrathin titanium liquid/gas diffusion layers (LGDLs) via a cost-effective and green chemical synthesis approach. The ultrathin integrated PtNW electrodes showed a low cell voltage of 1.643 V and high efficiency of 90.08% at 1000 mA cm -2 using about 15 times lower catalyst loadings than a conventional catalyst-coated membrane in PEMEC tests. Ex-situ electrochemical characterizations and microscale visualizations further reveal that PtNW electrodes display highly efficient hydrogen evolution reactions and excellent electrode durability due to high active surface area, favorable bubble detachment, and structural stability. This work provides new insights into catalyst layer design and facile ultrathin electrode fabrication for more compact and low-cost PEM electrolyzers, fuel cells and other systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗