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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 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Cross‐Coupling between Hydrazine and Aryl Halides with Hydroxide Base at Low Loadings of Palladium by Rate‐Determining Deprotonation of Bound Hydrazine

Abstract Reported here is the Pd‐catalyzed C–N coupling of hydrazine with (hetero)aryl chlorides and bromides to form aryl hydrazines with catalyst loadings as low as 100 ppm of Pd and KOH as base. Mechanistic studies revealed two catalyst resting states: an arylpalladium(II) hydroxide and arylpalladium(II) chloride. These compounds are present in two interconnected catalytic cycles and react with hydrazine and base or hydrazine alone to give the product. The selectivity of the hydroxide complex with hydrazine to form aryl over diaryl hydrazine was lower than that of the chloride complex, as well as the catalytic reaction. In contrast, the selectivity of the chloride complex closely matched that of the catalytic reaction, indicating that the aryl hydrazine is derived from this complex. Kinetic studies showed that the coupling process occurs by rate‐limiting deprotonation of a hydrazine‐bound arylpalladium(II) chloride complex to give an arylpalladium(II) hydrazido complex.

Wang, Justin Y.↗
DOE OSTI2022

Optimizing feed modulation for coupled methane and NO x conversion over Pd-Pt/Mn 0.5 Fe 2.5 O 4 /Al 2 O 3 monolith catalyst

Here the impacts of feed modulation (frequency, amplitude) and catalyst design (composition and architecture) parameters are reported for the conversion of methane and NO x over a dual-layer Pt+Pd/Al 2 O 3 + Mn 0.5 Fe 2.5 O 4 /Al 2 O 3 monolith. CH 4 and NO x conversion data show that the dual-layer catalyst outperforms single-layer samples having the same catalyst loadings, with and without spinel. Close proximity of the PGM and MFO functions in the mixed-layer catalyst lowers the CH 4 conversion at high temperature while separating the PGM and spinel layers with an intermediate Al 2 O 3 layer does not. Methane conversion enhancement is linked to its nonmonotonic dependence on O 2 . The performance gains are tied to a transient activity spike that occurs during the lean-to-rich feed transition when water is present in the feed. The transient spike is attributed to the removal of CO and H 2 products via reactions with stored O 2 in the spinel, eliminating inhibition of methane steam reforming.

03 NATURAL GAS↗
DOE OSTI2026

Mechanism-Informed Breakdown: Understanding Degradation by Controlling Voltage-Hold Patterns in Proton Exchange Membrane Water Electrolyzers

Low catalyst loadings pose challenges to performance stability in proton exchange membrane (PEM) water electrolysis over extended operation. To study the impact of degradation mechanisms and voltage loss rates, different stress tests are applied to membrane electrode assemblies. Potential cycling conditions were observed to induce higher degrees of iridium (Ir) oxide crystallization, ionomer degradation, and catalyst layer (CL) thinning, which likely contributed to higher kinetic loss rates. On the other hand, while Ir migrating into the PEM (Ir band) generally impairs performance, the interconnected and more uniform Ir band formed under a constant 2 V hold may allow for Ir at the catalyst/membrane interface to remain electronically connected and kinetically accessible, as well as indicate greater Ir site access during the applied stressor. The 2 V hold also demonstrates improved kinetic durability through a lower Tafel slope, faster polarization kinetics, and reduced charge transfer resistance. In contrast, potential cycling caused the migration of disconnected Ir agglomerates into the membrane bulk and created a steady increase in charge transfer resistance, a more dramatic decrease in capacitance (46.7% loss), and significant damage to the surrounding ionomer, indicating a decline in both the quality and quantity of active sites in the anode CL. This work underscores the distinct degradation pathways associated with load holds versus cycling, highlighting the role of catalyst-ionomer interactions in kinetic performance and long-term stability. These insights can inform operational strategies for PEM electrolyzers powered by intermittent energy sources, aiming to minimize efficiency losses over extended operation.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Low‐PGM and PGM‐Free Catalysts for Proton Exchange Membrane Fuel Cells: Stability Challenges and Material Solutions

Abstract Fuel cells as an attractive clean energy technology have recently regained popularity in academia, government, and industry. In a mainstream proton exchange membrane (PEM) fuel cell, platinum‐group‐metal (PGM)‐based catalysts account for ≈50% of the projected total cost for large‐scale production. To lower the cost, two materials‐based strategies have been pursued: 1) to decrease PGM catalyst usage (so‐called low‐PGM catalysts), and 2) to develop alternative PGM‐free catalysts. Grand stability challenges exist when PGM catalyst loading is decreased in a membrane electrode assembly (MEA)—the power generation unit of a PEM fuel cell—or when PGM‐free catalysts are integrated into an MEA. More importantly, there is a significant knowledge gap between materials innovation and device integration. For example, high‐performance electrocatalysts usually demonstrate undesired quick degradation in MEAs. This issue significantly limits the development of PEM fuel cells. Herein, recent progress in understanding the degradation of low‐PGM and PGM‐free catalysts in fuel cell MEAs and materials‐based solutions to address these issues are reviewed. The key factors that degrade the MEA performance are highlighted. Innovative, emerging material concepts and development of low‐PGM and PGM‐free catalysts are discussed.

Du, Lei↗
DOE OSTI2025

Foundation Models for Zero-Shot Segmentation of Scientific Images without AI-Ready Data

Zero-shot and prompt-based models have excelled at visual reasoning tasks by leveraging large-scale natural image corpora, but they often fail on sparse and domain-specific scientific image data. We introduce Zenesis, a no-code interactive computer vision platform designed to reduce data readiness bottlenecks in scientific imaging workflows. Zenesis integrates lightweight multimodal adaptation for zero-shot inference on raw scientific data, human-in-the-loop refinement, and heuristic-based temporal enhancement. We validate our approach on Focused Ion Beam Scanning Electron Microscopy (FIB-SEM) datasets of catalyst-loaded membranes. Zenesis outperforms baselines, achieving an average accuracy of 0.947, Intersection over Union (IoU) of 0.858, and Dice score of 0.923 on amorphous catalyst samples; and 0.987 accuracy, 0.857 IoU, and 0.923 Dice on crystalline samples. These results represent a significant performance gain over conventional methods such as Otsu thresholding and standalone models like the Segment Anything Model (SAM). Zenesis enables effective image segmentation in domains where annotated datasets are limited, offering a scalable solution for scientific discovery.

Mukherjee, Shubhabrata↗
DOE OSTI2023

Advanced electrode manufacturing to enable low cost PEM electrolysis

A critical challenge for the implementation of proton exchange membrane (PEM)-based water electrolyzers for the H2@Scale vision is the capital cost, which is largely driven by related factors of overdesign and highly manual legacy manufacturing methods. Typical electrolyzer cells have an order of magnitude higher membrane thickness and catalyst loading vs. fuel cells, in part because the manufacturing methods being used are not capable of producing uniform and reliable electrodes on thin membranes with low loading. Advanced electrode manufacturing is therefore the key enabler to reduce the cost of the electrolyzer stack, particularly roll-to-roll (R2R) manufacturing of catalyst coated layers (CCLs) and catalyst coated membranes (CCMs). The electrolyzer manufacturing process still relies on traditional sheet-to-sheet (S2S) processes, which requires intensive labor to make parts to meet the specification requirements. This project leverages fuel cell expertise (GM) with Proton’s knowledge of electrolyzer components to develop the electrocatalyst ink formulations and coating processes using slot die (ORNL) and gravure (NREL) coatings, with proof of concept at the pilot-scale (Kodak).

08 HYDROGEN↗
DOE OSTI2026

Surface-Initiated Atom Transfer Radical Polymerization Using Hydrogel Reactors

Atom transfer radical polymerization (ATRP) is a controlled radical polymerization method that enables the synthesis of tailored polymeric materials with low dispersity, highlighting its immense potential for green fabrication of advanced materials. However, its broader implementation is limited by challenges in product isolation, maintaining catalyst activity, and mitigating atmospheric sensitivity arising from oxygen-sensitive metal catalysts. Here, gelatin hydrogels (GHs) are introduced as a soft “reactor” matrix for interfacial ATRP, operating with minimal metal-catalyst loading while exhibiting possibly an organoreductive behavior. This strategy leverages activator regeneration via electron transfer through a ligand–metal charge-transfer (LMCT) mechanism to reduce oxidized metal catalysts within the GH network. Polymerization is evaluated by growing polymer brushes at an active interface formed between GHs swollen in monomer solution and an initiating surface, and sequential growth experiments confirmed that GH-mediated ATRP preserves living character. Under UV illumination, LMCT is activated, producing polymers both at the desired interface and within the GH bulk. UV–Vis spectroscopy revealed active reduction of Cu(II) to Cu(I) along with concentration-dependent complex formation, indicating dynamic coordination chemistry within the hydrogel. The redox-active arginine- and glutamic acid-rich gelatin backbone coordinates and reduces the metal center, enabling ATRP at ppm-level catalyst concentrations. While polymerization proceeds in GH-Cu(II) reactors, adding external mobile ligands to the GH results in longer polymer brushes. Here, the results reported here are exploratory. More experiments are needed to characterize polymer brush growth in GHs and compare it to conventional surface-initiated polymerization in solution.

Absorption↗
DOE OSTI2025

A dual promotional effect of doping tantalum (Ta) in atomically dispersed Ru/CeO 2 catalyst toward CO 2 methanation: Enhanced associative adsorption of CO 2 and activation of H 2

Precisely controlling the product selectivity in CO 2 hydrogenation through rational catalyst design presents a promising approach to mitigate environmental and energy-related challenges, though it remains a significant scientific hurdle. Herein, the CH 4 selectivity of 0.5 wt% Ru loaded catalysts at 250 °C was effectively shifted from approximately 35 % to 100 % through the incorporation of Ta dopant into the CeO 2 support. The EXAFS spectra in conjunction with CO DRIFTS experiment indicated the presence of atomically dispersed Ru particles anchored on the Ta-doped CeO 2 surface. A higher oxidized CeO 2 surface was evidenced in the presence of Ta dopant. The presence of Ta dopant also improved the dispersion of Ru species and their interaction with the support. Most importantly, the Ru/Ta-CeO 2 catalyst exhibited a pronounced capacity for associative CO 2 -adsorption under atmospheric pressure at 50 °C. An improved H 2 activation was also observed under CO 2 hydrogenation conditions. This novel finding of the dual promotional effect of Ta carries a significant impact in the field of CO 2 capture and utilization.

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

Degradation Mechanisms in Advanced MEAs for PEM Water Electrolyzers Fabricated by Reactive Spray Deposition Technology

Proton exchange membrane water electrolyzers (PEMWEs) have demonstrated enormous potential as the next generation hydrogen production technology. The main challenges that the state-of-the-art PEMWEs are currently facing are excessive cost and poor durability. Understanding the failure modes in PEMWEs is a key factor for improving their durability, lowering the precious metal loading, and hence cost reduction. Here, reactive spray deposition technology (RSDT) has been used to fabricate a membrane electrode assembly (MEA) with one order of magnitude lower Pt and Ir catalyst loadings (0.2–0.3 mg PGM cm –2 ) in comparison to the precious metal loadings in the stat-of-the-art commercial MEAs (2–3 mg PGM cm –2 ). As fabricated MEA with an active area of 86 cm 2 , has been tested for over 5000 h at steady-state conditions that are typical for an industrial hydrogen production system. Herein, we present and discuss the results from a comprehensive post-test analysis of the MEA of interest. The main degradation mechanisms, governing the performance loss in the RSDT fabricated MEA with ultra-low precious metal loadings, have been identified and discussed in detail. All failure modes are critically compared and the main degradation mechanism with the highest impact on the MEA performance loss among the others is identified.

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

Current Status on the Manufacturing of Nanomaterials for Proton Exchange Membrane Energy Systems by Vapor-Based Processes

Development of novel technologies for catalyst synthesis and membrane electrode assembly (MEA) fabrication is of primary importance for further improvement of the performance and economics of proton exchange membrane fuel cells (PEMFCs) and proton exchange membrane water electrolyzers (PEMWEs). While the traditional manufacturing methods are time-consuming, energy intensive, and require many processing steps, the new vapor-based methods provide many benefits including the development of improved catalysts and catalyst supports, deposition of uniform thin films, reduction of catalyst loading, and minimizing the number of manufacturing steps. Recent publications in the field identified spray pyrolysis, reactive spray deposition technology, chemical vapor deposition, and atomic layer deposition as advanced vapor-based catalyst synthesis and deposition methods used for fabrication of MEAs for PEMFCs and PEMWEs. Here, the MEAs fabricated via vapor-based processes have shown significant performance improvements in comparison to the state-of-the-art MEAs, which are attributed to better catalyst distribution, improved catalyst supports, and controlled, uniform catalyst layer microstructures. This review provides an overview of the vapor-based synthesis and deposition methods currently being used for the development of PEM-based devices. The advantages and disadvantages of these methods are critically compared and discussed while the outlook for future development is provided.

25 ENERGY STORAGE↗
DOE OSTI2025

Chemical Recycling of Polycaprolactones via Reactive Melt Processing

Chemical recycling is a promising technology for the deconstruction of waste plastics into monomers or other chemical intermediates, which can be converted into other value-added products or repolymerized into polymers. In this work, polycaprolactone and poly(4-propylcaprolactone) were chemically recycled by exploiting ring-closing depolymerization (RCD). To demonstrate the utility of this approach, reactive distillation experiments were initially conducted in a heated round-bottom flask with a distillation head to explore the effect of temperature and catalyst loading on RCD. Inspired by industrial devolatilization equipment, analogous experiments were conducted using a twin-screw melt compounder that was modified to simultaneously heat and mix polymer in the presence of a catalyst while continuously removing the evolved monomer vapors with a vacuum system and collecting them in a cold trap. Yield and selectivity of the recovered monomer were characterized by 1 H nuclear magnetic resonance spectroscopy and gas chromatography-mass spectrometry. Importantly, the more scalable twin-screw melt compounder approach produced values of monomer selectivity (∼90%) and yield (∼80%) similar to those of the round-bottom flask experiments. The recovered monomers were also successfully repolymerized into the same neat polymer with comparable molar masses without purification steps or adding initiator. Here, the results of this study promote the use of reactive devolatilization extrusion as a scalable approach to polyester depolymerization.

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

Theoretical Prediction and Experimental Verification of IrO x Supported on Titanium Nitride for Acidic Oxygen Evolution Reaction

Reducing iridium (Ir) catalyst loading for acidic oxygen evolution reaction (OER) is a critical strategy for large-scale hydrogen production via proton exchange membrane (PEM) water electrolysis. However, simultaneously achieving high activity, long-term stability, and reduced material cost remains challenging. To address this challenge, we develop a frame-work by combining density functional theory (DFT) prediction using model surfaces and proof-of-concept experimental ver-ification using thin films and nanoparticles. DFT results predict that oxidized Ir monolayers over titanium nitride (IrO x /TiN) should display higher OER activity than IrO x while reducing Ir loading. Further, this prediction is verified by depositing Ir monolayers over TiN thin films via physical vapor deposition. The promising thin film results are then extended to commercially viable powder IrO x /TiN catalysts, which demonstrate a lower overpotential and higher mass activity than commercial IrO 2 , and a long-term stability of 250 hours to maintain a current density of 10 mA cm -2 . The superior OER performance of IrO x /TiN is further confirmed using proton exchange membrane water electrolyzer (PEMWE), which shows a lower cell voltage than commercial IrO 2 to achieve a current density of 1 A cm -2 . Both DFT and in situ X-ray absorption spectroscopy reveal that the high OER performance of IrO x /TiN strongly depends on the IrO x - TiN interaction via direct Ir-Ti bonding. This study highlights the importance of close interaction between theoretical prediction based on mechanistic understanding and experimental verification based on thin film model catalysts to facilitate the development of more practical powder IrO x /TiN catalysts with high activity and stability for acidic OER.

08 HYDROGEN↗
DOE OSTI2023

Three-way catalyst with reduced palladium loading and method of making the three-way catalyst

A three-way catalyst for reduced palladium loading is provided. The catalyst includes an inert substrate and a palladium catalyst material coating the substrate. The palladium catalyst material includes a support material formed from one of 10% CeO 2 /Al 2 O 3 , 20% CeO 2 —Al 2 O 3 (20CeAlOy), 30% CeO 2 —Al 2 O 3 (30CeAlOy), Al 2 O 3 , and MOx-Al 2 O 3 , wherein M is one of copper, iron, manganese, titanium, zirconium, magnesium, strontium, and barium. The palladium catalyst material includes a layer of CeO 2 material disposed upon the support material, wherein the layer of CeO 2 material is dispersed on a surface of the support material. The palladium catalyst material includes an active component including a layer of praseodymium oxide particles dispersed across the surface of the layer of CeO 2 material and a layer of palladium particles disposed upon and dispersed across the surface of the layer of CeO 2 material at locations each corresponding to a respective location of each of the praseodymium particles.

Gu, Yuntao↗
DOE OSTI2025

Quantifying Sources of Voltage Decay in Long-Term Durability Testing for PEM Water Electrolysis

Meeting a competitive 1$/kg hydrogen cost target for polymer electrolyte membrane water electrolysis (PEMWE) will require advances to significantly reduce capital costs and precious metal catalyst usage, while simultaneously enabling 40,000–80,000 h stack lifetimes under dynamic use conditions. Minimizing cell voltage decay rates is therefore a key goal for PEMWE, although the fundamental processes governing voltage decay are not yet well understood. Here we present a quantitative approach to analyze the contributions to voltage decay in long-term PEMWE testing using polarization curves, impedance spectroscopy, and post-mortem electron microscopy. We apply this approach to analyze a 28 μV h −1 decay rate observed in a 4000 h durability test of a cell using 0.5 mg cm −2 total PGM catalyst loading (0.4 mg Ir cm −2 anode, 0.1 mg Pt cm −2 cathode) and 3 A cm −2 current density. We also analyze a comparative series of 1000 h tests under different conditions. These results provide valuable insights into anode catalyst degradation processes, as well as transferrable methodology for PEMWE durability research.

08 HYDROGEN↗
DOE OSTI2025

Advanced Catalysts for Olefin Synthesis: Copper(II) Quinoline-Fused Oxazolidines in Alcohol Dehydration

The new copper(II) catalyst [Cu( Q FOX)- (CH 3 CN)][OTf] 2 has been synthesized and found to be active for alcohol dehydration to give olefins at 120 °C with a 1% catalyst loading ( Q FOX = di-2-quinolinyl-fused-oxazolidine). Benzylic, allylic, and tertiary alcohols are all dehydrated. In some cases, ethers are observed to be produced, but these are re-entrained into the catalytic cycle. Unactivated secondary alcohols are also dehydrated. Similar catalysts employing Mn II , Fe II , Co II , and Ni II were also synthesized but showed reduced dehydration activity compared to the copper(II) derivative. A Cu I analog was also prepared but did not show improved dehydration activity.

Alcohols↗
DOE OSTI2021

Recent advances in integrating platinum group metal-free catalysts in proton exchange membrane fuel cells

Platinum group metal (PGM)-free catalysts are promising low-cost materials for the oxygen reduction reaction in proton exchange membrane fuel cells (PEMFCs). A variety of chemical precursors and synthesis methods have been proposed to increase their catalytic activity. In comparison, significantly less attention has been dedicated to the integration of these PGM-free catalysts into operating electrodes by investigating the role of the membrane electrode assembly (MEA) fabrication on the PEMFC performance. Here, we discuss here some remarkable performance improvements recently achieved by tuning catalyst loading, ionomer content, and ink solvent composition, and call for further explorations of the ink processing and MEA fabrication to improve performance.

25 ENERGY STORAGE↗
DOE OSTI2025

Photo-Induced Hydrogen Production from Formic Acid Using a Palladium Catalyst

Liquid organic hydrogen carriers (LOHCs) are recognized as promising sustainable hydrogen (H 2 ) carriers due to their high volumetric capacity and ability to store H 2 at ambient conditions, eliminating the need for energy-intensive liquefaction or compression processes associated with H 2 or ammonia gas. One of the main current drawbacks, however, is LOHCs’ high energy demand for H 2 release. This work presents the photo-induced liberation of H 2 from formic acid (FA) as a liquid H 2 carrier, using visible light and well-established 5 wt% palladium nanoparticles supported over carbon (Pd/C). We show that low-power light-emitting diodes (LEDs) produced higher gas flow than their thermal baseline (35 °C), with 27.2 mL/min and 7.72 mL/min, respectively. Further, the rate of gas evolved with light intensity, catalyst loading, and the concentration of FA. Light-induced dehydrogenation shows similar deactivation as the known thermal mechanisms, such as the decreased Pd 2+ /Pd 0 ratio and Pd nanoparticle agglomeration. Hence, these observations suggest a photothermal mechanism, whereby the LED provides heat efficiently absorbed by the Pd/C catalyst and enhanced by Pd’s ability to absorb light, thereby driving the FA dehydrogenation reaction at ambient conditions.

08 HYDROGEN↗