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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 451 records · Page 25
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Fine Gradient Electrode and Micro Porous Layer Structures for Improved Heavy Duty Fuel Cells (Final Report)

The commercial deployment of Heavy Duty Fuel Cells(HDFC) for applications such as large trucks (for example, Class 8 capable of carrying 50,000 lb. loads) depends vitally on achieving high efficiency and durability at reasonable costs. Furthermore, the HDFC must operate under practical conditions such as with fuel and air impurities, multiple stop-start cycles, and under the extremes of climate our planet offers – from hot and cold to dry and wet. These conditions place a premium on the stability and utilization of the materials comprising the membrane electrode assemblies (MEAs) powering the fuel cell. and the current catalysts, MicroPorous Layers, and Electrode structures and additives are insufficient for these needs. In Phase I Pajarito and Advent will develop durable electrocatalysts, MicroPorous Layer and electrode additives, and electrode structures for heavy duty fuel cells designed for zero-emission long-haul trucking. The electrocatalyst products are designed to solve the challenging durability and performance needs of fuel cells designed for long life and high efficiency through a combination of uniquely structured designed catalysts as well as new MicroPorous Layers (MPLs) and electrode structure additives. These improved materials will provide Pajarito both an expanded commercial opportunity in electrocatalysts, as well as new markets for MPL and electrode additives. The resulting public benefits include improved economics of fuel cells, a leading zero-emission technology for mobility, as well as reduced reliance on the critical minerals and metals used in the heavy-duty trucks industry. Possible follow-up Phase II and III projects would add full MEA products based on the Phase I efforts catalysts and additives, with full system validation by leading Fuel Cell Truck developers.

08 HYDROGEN↗
DOE OSTI2020

Effect of Dispersion Medium Composition and Ionomer Concentration on the Microstructure and Rheology of Fe–N–C Platinum Group Metal-free Catalyst Inks for Polymer Electrolyte Membrane Fuel Cells

In this paper, we present an investigation of the microstructure and rheological behavior of catalyst inks consisting of Fe–N–C platinum group metal-free catalysts and a perfluorosulfonic acid ionomer in a dispersion medium (DM) of water and 1-propanol ( n PA). The effects of the ionomer-to-catalyst (I/C) ratio and weight percentage of water (H 2 O %) in the DM on the ink microstructure were studied. Steady-shear and dynamic-oscillatory-shear rheology, in combination with synchrotron X-ray scattering, was utilized to understand interparticle interactions and the level of agglomeration of the inks. In the absence of the ionomer, the inks were significantly agglomerated, approaching a gel-like microstructure for catalyst concentrations as low as 2 wt %. The effect of H 2 O % in the DM on particle agglomeration was found to vary with particle concentration. In concentrated inks (≥2 wt % catalyst), increasing H 2 O % was found to increase agglomeration because of the hydrophobic nature of the catalysts. In dilute inks (<1 wt % catalyst), the trend was reversed with increasing H 2 O %, suggesting that electrostatic interactions are dominating the behavior. In inks with 5 wt % catalyst, the addition of an ionomer was found to significantly stabilize the catalyst against agglomeration. Maximum stability was observed at 0.35 I/C for all DM H 2 O % studied. At high ionomer concentrations (I/C > 0.35), interesting differences were observed between n PA-rich inks (H 2 O % ≤ 50%) and H 2 O-rich (82% H 2 O) inks. The n PA-rich inks remained predominantly stable—ink viscosity only weakly increased with I/C and the Newtonian behavior was maintained for I/C up to 0.9. In contrast, the H 2 O-rich inks exhibited a significant increase in viscoelasticity with increasing I/C, suggesting flocculation of the catalyst by the ionomer. These differences suggest that the nature of the interactions between the ionomer and catalyst is highly dependent on the H 2 O % in the DM.

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

Zero-Valent Palladium Single-Atoms Catalysts Confined in Black Phosphorus for Efficient Semi-Hydrogenation

Single-atom catalysts (SACs) represent a new frontier in heterogeneous catalysis due to their remarkable catalytic properties and maximized atomic utilization. However, single atoms often bond to the support with polarized electron density and thus exhibit a high valence state, limiting their catalytic scopes in many chemical transformations. In this study, it is demonstrated that 2D black phosphorus (BP) acts as giant phosphorus (P) ligand to confine a high density of single atoms (e.g., Pd 1 , Pt 1 ) via atomic layer deposition. Unlike other 2D materials, BP with relatively low electronegativity and buckled structure favors the strong confinement of robust zero-valent palladium SACs in the vacancy site. Metallic Pd 1 /BP SAC shows a highly selective semi-hydrogenation of phenylacetylene toward styrene, distinct from metallic Pd nanoparticles that facilitate the formation of fully hydrogenated products. Density functional theory calculations reveal that Pd atom forms covalent-like bonding with adjacent P atoms, wherein H atoms tend to adsorb, aiding the dissociative adsorption of H 2 . Zero-valent Pd in the confined space favors a larger energy gain for the synthesis of partially hydrogenated product over the fully hydrogenated one. This work provides a new route toward the synthesis of zero-valent SACs on BP for organic transformations.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Trace levels of PtRu on NiMo foam electrodes towards hydrogen evolution reaction

Electrochemical water splitting plays a critical role in high purity hydrogen production. To lower capital cost and energy consumption, efficient catalysts are required to boost the hydrogen evolution reaction (HER), especially in alkaline media. Although PtRu alloy materials are still considered the state-of-the-art catalyst for the HER under alkaline media, large-scale application is hindered by its scarcity and high cost. NiMo alloy catalysts can be potential Pt-free alternatives to drive the sluggish kinetics of the HER under alkaline media, but their HER activity is still not ideal due to the limitation of Volmer step. Herein, we investigated the impact of trace levels of PtRu catalysts on NiMo electrodes towards the HER by incorporating advantages of both PtRu and NiMo catalysts to minimize cost and maintain a promising HER activity. Trace levels of PtRu catalysts from 0.0173 to 0.2648 mg cm −2 were loaded on commercial NiMo foam electrodes by a facile electrodeposition technique utilizing ppm concentration levels of PtRu in electrolyte. The results show that 0.0173 mg cm −2 PtRu loading on NiMo electrode can significantly enhance HER activity compared to the pristine NiMo foam electrode (Tafel slopes drop from ∼170 to ∼60 mV dec −1 ) due to the remarkable decline of energy barriers towards water dissociation and hydrogen adsorption. Meanwhile, the rate determining step (RDS) switches from the Volmer step to the Heyrovsky step when the PtRu loading increases to 0.0675 mg cm −2 . Promising catalytic stability is observed at 100 mA cm −2 over the course of 50 h with a PtRu loading of 0.1198 mg cm −2 . In conclusion, this work demonstrates a potential strategy to decrease the cost and simultaneously maintain superior HER performance by integrating trace levels of PtRu catalyst with NiMo foam electrodes.

Electrochemical water splitting↗
DOE OSTI2020

Production of C 2 /C 3 Oxygenates from Planar Copper Nitride-Derived Mesoporous Copper via Electrochemical Reduction of CO 2

Electrochemical reduction of CO 2 provides an opportunity to produce fuels and chemicals in a carbon-neutral manner, assuming that CO 2 can be captured from the atmosphere. To do so requires efficient, selective, and stable catalysts. In this study, we report a highly mesoporous metallic Cu catalyst prepared by electrochemical reduction of thermally nitrided Cu foil. Under aqueous saturated CO 2 reduction conditions, the Cu 3 N-derived Cu electrocatalyst produces virtually no CH 4 , very little CO, and exhibits a faradaic efficiency of 68% in C 2+ products (C 2 H 4 , C 2 H 5 OH, and C 3 H 7 OH) at a current density of ~18.5 mA cm –2 and a cathode potential of -1.0 V versus the reversible hydrogen electrode. Under these conditions, the catalyst produces more oxygenated products than hydrocarbons. We show that surface roughness is a good descriptor of catalytic performance. The roughest surface reached 98% CO utilization efficiency for C 2+ product formation from CO 2 reduction and the ratio of oxygenated to hydrocarbon products correlates with the degree of surface roughness. These effects of surface roughness are attributed to the high population of undercoordinated sites as well as a high pH environment within the mesopores and adjacent to the surface of the catalyst.

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

Durability of Pt-Alloy Catalyst for Heavy-Duty Polymer Electrolyte Fuel Cell Applications under Realistic Conditions

As an emerging technology, polymer electrolyte fuel cells (PEFCs) powered by clean hydrogen can be a great source of renewable power generation with flexible utilization because of high gravimetric energy density of hydrogen. To be used in real-life applications, PEFCs need to maintain their performance for long-term use under a wide range of conditions. Therefore, it's important to understand the degradation of the PEFC under protocols that are closely related to the catalyst lifetime. Alloying Pt with transitional metal improves catalyst activity. It is also crucial to understand Pt alloys degradation mechanisms to improve their durability. To study durability of Pt alloys, accelerated stress tests (ASTs) are performed on Pt-Co catalyst supported on two types of carbon. Two different AST protocols were being studied: Membrane Electrolyte Assembly (MEA) AST based on the protocol introduced by the Million Mile Fuel Cell Truck consortium in 2023 and Catalyst AST, adopted from the U.S. Department of Energy (DoE).

25 ENERGY STORAGE↗
DOE OSTI2023

Bifunctional porous non-noble metal phosphide catalyst for overall water splitting and methods of making and using same

A method of electrocatalytic water splitting by providing an anode and a cathode; and utilizing the anode and the cathode for alkaline water electrolysis. Each of the anode and the cathode comprises a uniform distribution of a bifunctional electrocatalyst comprising metallic phosphides on a conductive substrate. The metallic phosphides comprise arion phosphide (FeP) and dinickel phosphide (Ni 2 P). The bifunctional electrocatalyst promotes hydrogen evolution reaction (HER) at the cathode, and oxygen evolution reaction (OER) at the anode.

Ren, Zhifeng↗
DOE OSTI2021

Advanced Nanocarbons for Enhanced Performance and Durability of Platinum Catalysts in Proton Exchange Membrane Fuel Cells

Insufficient stability of current carbon supported Pt and Pt alloy catalysts is a significant barrier for proton-exchange membrane fuel cells (PEMFCs). As a primary degradation cause to trigger Pt nanoparticle migration, dissolution, and aggregation, carbon corrosion remains a significant challenge. Compared with enhancing Pt and PtM alloy particle stability, improving support stability is rather challenging due to carbon's thermodynamic instability under fuel cell operation. In recent years, significant efforts have been made to develop highly durable carbon-based supports concerning innovative nanostructure design and synthesis along with mechanistic understanding. Here, this review critically discusses recent progress in developing carbon-based materials for Pt catalysts and provides synthesis–structure–performance correlations to elucidate underlying stability enhancement mechanisms. The mechanisms and impacts of carbon support degradation on Pt catalyst performance are first discussed. The general strategies are summarized to tailor the carbon structures and strengthen the metal–support interactions, followed by discussions on how these designs lead to enhanced support stability. Based on current experimental and theoretical studies, the critical features of carbon supports are analyzed concerning their impacts on the performance and durability of Pt catalysts in fuel cells. Finally, the perspectives are shared on future directions to develop advanced carbon materials with favorable morphologies and nanostructures to increase Pt utilization, strengthen metal-support interactions, facilitate mass/charge transfer, and enhance corrosion resistance.

25 ENERGY STORAGE↗
DOE OSTI2022

Developing reactors for electrifying bio-methanation: a perspective from bio-electrochemistry

The integration of microbial synthesis with renewable electricity is an emerging route for both CO 2 utilization and seasonal energy storage in the form of stored bio-electrofuels. The major benefits of electrifying bioreactors include: using highly selective bio-catalysts for CO 2 conversion under mild reaction conditions; decoupling the production of more facile electrochemical intermediates, such as hydrogen, at the electrode from the production of bio-catalyzed multi-electron and/or carbon products, such as methane or acetate; using microbes as robust and self-regenerating catalysts enabling higher efficiency and durability in CO 2 conversion systems compared to inorganic catalysis. In this Perspective, we propose research aimed at developing electro-bioreactor components that will increase the productivity of the reactor while maintaining high energy efficiency and biocompatible reaction conditions to fully realize the benefits of electrified bioreactors. Furthermore, these developments include: flow reactors with tailored 3D electrodes to optimally use the reactor volume, electrocatalysts designed for peak performance in neutral pH electrolytes, high conductivity microbial media, and new membrane separator materials with high ion conductivity and low gas permeability. Production of methane via a hybrid electrical-biological approach is taken as a case study to motivate these developments. Finally, an iterative design–manufacture–test cycle, enabled by additive manufacturing and 3D printing technologies, is proposed to rapidly prototype components prior to large-scale manufacturing.

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

Effect of Electrochemical Oxidation on Physicochemical Properties of Fe-Containing Single-Walled Carbon Nanotubes

Metal catalysts are necessary for fabricating carbon nanotubes, but are often considered impurities in the end products, and arduous steps are used to remove catalyst residues from the nanotube structure. However, as metals can be electrocatalytic, instead of removing them we can utilize their role in detection of analgesics. Herein, we study the physicochemical properties of Fe-containing single-walled carbon nanotubes (SWCNTs), and the effect of simple oxidative pretreatment on them. We show that a gentle anodic pretreatment i) increased the amount of oxidized Fe nanoparticles, most likely exhibiting phases Fe3O4 and Fe2O3 and ii) effectively removed disordered carbonaceous material from SWCNT bundles surfaces. Pretreatment had only a marginal effect on sensitivity towards analgesics. However, interestingly, selectivity of Fe-SWCNTs towards paracetamol and morphine could be modified with pretreatment. Through this kind of in-depth investigation, we can, to a certain extent, correlate various material properties of SWCNTs with the observed electrochemical performance. We show this approach allows us to evaluate what factors in SWCNTs truly affect the electrochemical detection of biomolecules.

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

Ultrafast Reaction Mechanisms in Perovskite Based Photocatalytic C–C Coupling

Solar driven carbon-carbon (C-C) bond formation is a new direction in solar energy utilization. Earth abundant nanocrystal based photocatalysts are highly sought after as they can potentially eliminate expensive noble metal catalysts. A detailed understanding of the underlying reaction mechanisms could provide guidance in designing new systems that can activate a larger class of small molecules. Here, we employ transient absorption spectroscopy to study a model C-C bond formation reaction, i.e., a-alkylation of aldehydes catalyzed by colloidal CsPbBr3 nanocrystals (NCs). We find that both electrons and holes undergo ultrafast charge transfer (~50 ps) from photoexcited perovskite NCs to reactant molecules. A charge separated state lives for more than 0.8 µs, enabling a radical mechanism to form the C-C bonds. We discuss the differences between the NCs photoredox catalysts and the molecular catalyst.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Ionic functionalization of aromatic polymers for ion exchange membranes

The electrochemical energy conversion system of the present disclosure includes an anode, a cathode, and an ion exchange membrane including a polymer having an aromatic polymer chain and an alkylated substrate including an alkyl chain, and at least one ionic group. The alkylated substrate is bound to at least one aromatic group in the polymer chain via Friedel-Crafts alkylation of the at least one aromatic group. The alkylation reaction utilizes a haloalkylated tertiary alcohol or a haloalkylated alkene as a precursor. In the presence of an acid catalyst, a carbocation is generated in the precursor which reacts with the aromatic rings of the polymer chain. The at least one ionic group is then replaced with a desired cationic or anionic group using a substitution reaction. The membranes exhibit advantageous stability achieved through a simplified and scalable reaction scheme.

Bae, Chulsung↗
DOE OSTI2025

Studying the Durability of Molybdenum Carbide Aerogel as an Electrocatalyst Support for Proton Exchange Membrane Fuel Cells

Carbon-supported platinum nanoparticles (Pt/C) are currently the state-of-the-art catalyst in proton exchange membrane fuel cells (PEMFCs). Unfortunately, the carbon support lacks the ability to stabilize the metal catalyst, as platinum tends to dissolve and agglomerate, significantly compromising the durability. Herein, we synthesized a ceramic material, molybdenum carbide aerogel (MCAG), and utilized it as a Pt support for PEMFCs, as an alternative for conventional carbon supports. N 2 adsorption and XRD analysis showed that the MCAG possesses a combination of high porosity and a well-defined ceramic crystalline structure. The Pt/MCAG system was studied for its electrocatalytic activity toward ORR in a half-cell and demonstrated satisfactory reaction kinetics and electrochemical active surface area, comparable to the commercial Pt/C. For durability examination, an accelerated stress test (AST) in a single cell was conducted with the Pt/MCAG catalyst at the cathode, following the U.S. DOE electrocatalyst AST protocol. Intermediate polarization curves and cyclic voltammograms were recorded over the course of the AST to monitor the aging process. The results indicated that the MCAG support exhibited superior durability in long-term fuel cell operation compared to a carbon support. The Pt/MCAG system demonstrated stable behavior during the progressive stages of the AST, retaining more than 50% of its initial performance by the end of the test, whereas carbon-supported Pt preserved only 30%.

25 ENERGY STORAGE↗
DOE OSTI2023

Surface Science Studies of Selective Fischer-Tropsch Chemistry on Cobalt Carbide Surfaces

Advances in catalysis science are critical to the progress of the United States. Catalysis is employed, in one way or another, in the production of almost every chemical and product manufactured. The catalysis research that we undertook here, regarding the role of specific facets of cobalt carbide in the Fischer-Tropsch production of low molecular weight olefins (FTO), is motivated by the work of many previous investigators. In particular two research groups from China had discovered FTO catalysts that work very selectively for low molecular weight olefins coupled with low production of methane. These are potentially very important findings that could find significant industrial utility if improvements can be discovered. With the research undertaken here we chose to focus on one of these studies and especially the Co 2 C surfaces that they implicate as being responsible for this exciting FTO catalysis with low production of methane. In this study, Zhong and co-workers investigated cobalt-manganese oxide catalysts for the Fischer-Tropsch to Olefins process. After reaching steady-state their catalyst showed a good selectivity to light olefins and low selectivity to methane with a carbon monoxide conversion of 31.8% at one atmosphere (with a H 2 /CO ratio of two and a temperature of 250°C). Lower H 2 /CO ratios and lower pressures increased the olefin production. Their catalyst characterization studies indicated that cobalt carbide quadrangular nanoprisms with preferentially exposed (101) and (020) facets were important in favoring lower olefin production and inhibiting methane formation. The authors stated that these cobalt carbide nanoprisms are a promising new catalyst system for directly converting synthesis gas to lower olefins. Motivated by the studies of Zhong and co-workers, our goal with the research here was to contribute to a better understanding of catalysis science through the study of surface chemical reactions related to the Fischer-Tropsch to Olefins reaction on specific facets of planar model cobalt carbide catalysts in ultrahigh vacuum.

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

Controlling Bond Scission Pathways of Isopropanol on Fe- and Pt-Modified Mo 2 N Model Surfaces and Powder Catalysts

Biomass valorization can be used to produce value-added chemicals and fuels from renewable biomass resources by upgrading them via selective bond scission while retaining certain functional groups. Specifically, upgrading biomass through the dehydrogenation of alcohols to carbonyl compounds has gained interest as a method of utilizing biomass-derived alcohols while additionally producing H 2 . In this work, isopropanol was used as a probe molecule to control bond scission selectivity over Fe- and Pt-modified molybdenum nitride (Mo 2 N) model surfaces and powder catalysts. Trends in the selectivity toward dehydration and dehydrogenation were dependent on both the type and coverage of the metal overlayer on model surfaces. These results were then extended to the corresponding powder catalysts to demonstrate how model surface studies can inform the design of supported catalysts. Density functional theory calculations provided insights into controlling the dehydration and dehydrogenation pathways. In conclusion, this work shows that a fundamental understanding of the reactivity and intermediates on Mo 2 N-based model surfaces can be applied to understand the catalytic performance of metal-modified Mo 2 N powder catalysts, and also demonstrates that Mo 2 N-based catalysts are potentially promising materials for upgrading biomass-derived oxygenates.

09 BIOMASS FUELS↗
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 OSTI2026

Impact of DMP-30 catalyst concentration on the degradation and kinetics of bisphenol A epoxy thermosets cured with linear amine hardener

Epoxy thermosets are a crucial component in carbon-fiber composites, serving as the organic binding matrix. Catalysts are commonly used in prepolymer formulations to accelerate curing of the thermosets. However, the impact of catalysts on the thermal stability, degradation pathways, and kinetics of the final thermoset is poorly understood. Here, in this work, Product-Specific Kinetics (PSK) analysis was utilized with isoconversional kinetics to provide a first look into the degradation kinetics of major pyrolysis pathways in bisphenol A (BPA) epoxy resins and determine the impact of altering catalysis concentrations on these kinetic pathways. Results revealed new insights into previously identified degradation pathways, provided evidence of multiple degradation pathways for some products, and showed that use of excess catalyst results in polymer network alterations and reduced thermal stability of the thermosets.

Bisphenol A↗