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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 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Carbon-Nanotube-Bridging Strategy for Integrating Single Fe Atoms and NiCo Nanoparticles in a Bifunctional Oxygen Electrocatalyst toward High-Efficiency and Long-Life Rechargeable Zinc–Air Batteries

The development of highly efficient and robust bifunctional electrocatalysts for oxygen reduction (ORR) and evolution reactions (OER) is the key issue for realizing high-performance and long-life rechargeable zinc–air batteries (ZABs). However, it is still a great challenge to integrate independent ORR and OER sites in a catalyst with high activity. Here, a carbon nanotube-bridging strategy is proposed to synthesize such a bifunctional oxygen electrocatalyst enriched with highly active single-atom Fe sites for the ORR and high-performance nanosized NiCo hydroxides for the OER. Consequently, the developed catalyst shows a small overpotential difference of 0.686 V. When used as an oxygen electrode catalyst, the corresponding ZAB exhibits a large power density of 219.5 mW cm ₋2 , a small charge–discharge voltage gap of 0.72 V at 10 mA cm ₋2 , and outstanding discharge–charge durability without attenuation after more than 700 cycles. This work proposes a new idea to realize multifunctional catalysts and drives the practical application of ZABs.

25 ENERGY STORAGE↗
DOE OSTI2024

Self-Sacrificial Template Synthesis of Fe-N-C Catalysts with Dense Active Sites Deposited on A Porous Carbon Network for High Performance in PEMFC

In this study, iron-nitrogen-carbon (Fe-N-C) single-atom catalysts are promising sustainable alternatives to the costly and scarce platinum (Pt) to catalyze the oxygen reduction reactions (ORR) at the cathode of proton exchange membrane fuel cells (PEMFCs). However, Fe-N-C cathodes for PEMFC are made thicker than Pt/C ones, in order to compensate for the lower intrinsic ORR activity and site density of Fe-N-C materials. The thick electrodes are bound with mass transport issues that limit their performance at high current densities, especially in H 2 /air PEMFCs. Practical Fe-N-C electrodes must combine high intrinsic ORR activity, high site density, and fast mass transport. Herein, it has achieved an improved combination of these properties with a Fe-N-C catalyst prepared via a two-step synthesis approach, constructing first a porous zinc-nitrogen-carbon (Zn-N-C) substrate, followed by transmetallating Zn by Fe via chemical vapor deposition. A cathode comprising this Fe-N-C catalyst has exhibited a maximum power density of 0.53 W cm -2 in H 2 /air PEMFC at 80 °C. The improved power density is associated with the hierarchical porosity of the Zn-N-C substrate of this work, which is achieved by epitaxial growth of ZIF-8 onto g-C 3 N 4 , leading to a micro-mesoporous substrate.

25 ENERGY STORAGE↗
DOE OSTI2020

Enhancing Oxygen Reduction Activity of Pt-based Electrocatalysts: From Theoretical Mechanisms to Practical Methods

Pt-based electrocatalysts are considered as one of the most promising choices to facilitate the oxygen reduction reaction (ORR), and the key factor enabling their success is to reduce the required amount of platinum. Herein, we focus on illuminating both the theoretical mechanisms which enable enhanced and sustained ORR activity and the practical methods to achieve them in catalysts. The various multi-step pathways of ORR are firstly reviewed and the rate-determining steps based on the reaction intermediates and their binding energies are analyzed. We then explain the critical aspects of Pt-based electrocatalysts to tune oxygen reduction properties from the viewpoints of active sites exposure and altering the surface electronic structure, and further summarize representative research progress towards practically achieving these activity enhancements with a focus on platinum size reduction, shape control and core Pt elimination methods. Finally, we outline the remaining challenges and provide our perspectives with regard to further enhancing their activities.

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

Theoretical Investigation of the Oxygen Reduction Reaction over Platinum Catalysts Supported by Multi-Edged Vertically Aligned Carbon Nanofiber for Electrocatalyst Preparation

Vertically aligned carbon nanofibers (VACNFs) are promising supports for oxygen reduction reaction (ORR) electrocatalysts in fuel cells. Although experimentally these catalytic systems have shown great potential, there is lack of molecular understanding of the catalytic sites and reaction mechanisms. This work investigated the origin of the ORR reactivities of the platinum catalysts on multi-edged VACNFs (Pt/VACNF) using a multiscale modeling approach combining Density Functional Theory (DFT) and classical Molecular Dynamics (MD) simulations. Based on the ReaxFF potential, here all nanoscale Pt particles (Pt 55 , P 100 , and Pt 147 ) are stabilized by the open edges located axially along the VACNF walls. The calculated first-shell coordination numbers, CN, of surface Pt atoms are 6.63, 7.27, and 7.85, respectively, suggesting that the percentage of low coordination sites increases as the particle size decreases. The adsorption energies of OOH, O, and OH on Pt-55 were systematically probed using DFT calculations. These adsorption energies retain a linear correlation against the generalized coordination numbers ($\overline{CN}$). For Pt nanoparticles supported on VACNF, we found that the OOH and OH bind stronger than on Pt (111) by 0.14 and 0.17 eV, respectively, which can hinder the ORR activity with lower limiting potential than Pt (111). Our theoretical prediction is in good agreement with the linear sweeping voltammetry that revealed a left shift of the half-wave potential.

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

Understanding the Active Site Structures and Achieving Catalytic Activity Tuning of Atomically Dispersed FeN 4 Sites for Oxygen Reduction Reaction

Atomically dispersed Fe–—N—C catalysts with high oxygen reduction reaction (ORR) activity have attracted great attention since the last decade. Due to comparable ORR activity and low material cost, they are promising platinum group metal (PGM)-free catalysts that can replace the commercialized Pt/C materials; furthermore, it can facilitate the efficiency of the fuel cell technologies and mitigate dependence on fossil fuels. Great advancements have been made to experimentally optimize the synthesis approach of the Fe–—N—C catalysts, enhance the ORR activity, and improve the catalyst stability. Similarly, recent theoretical studies also provide enriched understanding of the active site structures, properties, and reaction mechanisms. In this review, discussions are made upon utilizing combined experimental and computational spectroscopy to reveal the active site structures, employing mechanistic studies to investigate reaction thermodynamics and kinetics, as well as developing scaling relationships to assist the design and development of future PGM-free catalyst materials. Furthermore, recent advances in studying Fe–—N—C catalysts utilizing electrified surface models and explicit solvation models are also discussed. Not only can these aspects improve the accuracy of theoretical simulation and predictions but also deepen the understanding of the catalyst properties and reaction mechanisms under the effect of surface charges and solvent molecules.

Fe single-atom catalysts↗
DOE OSTI2021

Metal–Nitrogen–Carbon Cluster–Decorated Titanium Carbide is a Durable and Inexpensive Oxygen Reduction Reaction Electrocatalyst

Clusters of nitrogen- and carbon-coordinated transition metals dispersed in a carbon matrix (e. g., Fe-N-C) have emerged as an inexpensive class of electrocatalysts for the oxygen reduction reaction (ORR). In this work, it was shown that optimizing the interaction between the nitrogen-coordinated transition metal clusters embedded in a more stable and corrosion-resistant carbide matrix yielded an ORR electrocatalyst with enhanced activity and stability compared to Fe-N-C catalysts. Utilizing first-principles calculations, an electrostatics-based descriptor of catalytic activity was identified, and nitrogen-coordinated iron (FeN 4 ) clusters embedded in a TiC matrix were predicted to be an efficient platinum-group metal (PGM)-free ORR electrocatalyst. Guided by theory, selected catalyst formulations were synthesized, and it was demonstrated that the experimentally observed trends in activity fell exactly in line with the descriptor-derived theoretical predictions. The Fe-N-TiC catalyst exhibited enhanced activity (20 %) and durability (3.5-fold improvement) compared to a traditional Fe-N-C catalyst. It was posited that the electrostatics-based descriptor provides a powerful platform for the design of active and stable PGM-free electrocatalysts and heterogenous single-atom catalysts for other electrochemical reactions.

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

Rapid microwave-assisted preparation of high-performance bifunctional Ni3Fe/Co-N-C for rechargeable Zn-air battery

Precious metal-free bifunctional catalysts offer scalable possibilities for achieving oxygen cathodes in rechargeable metal-air batteries. Literature thus far suggests that the oxygen reduction and evolution reactions (i.e ORR and OER) take place at different active sites. However, the design and preparation of oxygen electrocatalysts with high-performance is still a great challenge. This work develops a general approach to introduce a nanoparticle that offers oxygen evolution reaction sites onto an oxygen reduction reaction catalyst via rapid microwave treatment. The metal–organic frameworks (Co, ZIF-8) derived Co-N-C with high ORR performance is employed as a support to homogeneously disperse OER active Ni3Fe nanoparticles. Potentials of 1.54 V and 0.79 V have been achieved at current densities of 10 mA cm -2 for OER and 3 mA cm -2 toward ORR, respectively. The developed rechargeable Zn-air battery assembled with Ni 3 Fe/Co-N-C as an oxygen-electrode exhibits superior efficiency and robust durability, exceeding that of commercial Pt/C + IrO 2 . Furthermore, the satisfactory activity of our fabricated wristband shows the successfully practical application of flexible Zn-air batteries for wearable devices.

25 ENERGY STORAGE↗
DOE OSTI2020

Identification of the Electronic and Structural Dynamics of Catalytic Centers in Single-Fe-Atom Material

The lack of model single-atom catalysts (SACs) and atomic-resolution operando spectroscopic techniques greatly limits our comprehension of the nature of catalysis. Herein, based on the designed model single-Fe-atom catalysts with well-controlled microenvironments, we have explored the exact structure of catalytic centers and provided insights into a spin-crossover-involved mechanism for oxygen reduction reaction (ORR) using operando Raman, X-ray absorption spectroscopies, and the developed operando 57 Fe Mössbauer spectroscopy. In combination with theoretical studies, the N-FeN 4 C 10 moiety is evidenced as a more active site for ORR. Moreover, the potential-relevant dynamic cycles of both geometric structure and electronic configuration of reactive single-Fe-atom moieties are evidenced via capturing the peroxido (*O 2 -) and hydroxyl (*OH-) intermediates under in situ ORR conditions. Overall, we anticipate that the integration of operando techniques and SACs in this work shall shed some light on the electronic-level insight into the catalytic centers and underlying reaction mechanism.

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

Outstanding Platinum Group Metal-free Bifunctional Catalysts for Rechargeable Zinc-Air Batteries

Developing highly active and durable catalysts for zinc-air batteries (ZAB) is critical for energy conversion and storage. Herein, we prepared Fe-N-C catalysts at a kilogram scale by the commercial VariPore™ method and the effect of synthesis conditions on the catalyst performance at ZAB air electrode was investigated. The results show the PA-450-HT exhibits excellent electrocatalytic activity toward oxygen reduction reaction (ORR) and it is the most suitable catalyst for primary ZAB with the galvanostatic polarization discharge peak power density of 149 mW cm -2 , outperforming commercial Pt-Ru/C catalysts. Additionally, the NCB-600-HT catalyst displays the half-wave potential of 0.87 V vs. RHE for ORR and ΔE value of 0.81 V (indicating outstanding ORR and OER reversibility) and exhibits excellent charge-discharge cycling durability similar to NCB-550-LT around 160 h for the secondary ZAB. This work reports outstanding bifunctional Fe-N-C catalysts for rechargeable ZAB at mass production for the first time.

25 ENERGY STORAGE↗
DOE OSTI2023

Oxygen reduction reaction catalysts prepared by platinizing thermally activated zeolitic imidazolate frameworks

In this study, highly efficient and low-cost oxygen reduction reaction (ORR) catalyst is essential to improve the cost competitiveness of the proton-exchange membrane fuel cells (PEMFCs). One potential approach of cost reduction is to apply low loading Pt over a catalytically active support made of platinum metal group free (PGM-free) material to compensate the overall ORR activity through synergistic catalysis between Pt and PGM-free support. In this report, we investigated a series of catalysts prepared by adding low-loading Pt over ORR active support prepared through thermally activated Co/Zn methyl-imidazolate framework (Co/Zn-ZIF) at various Co/Zn ratios. Catalytic activity measurement and structural characterization were performed in an attempt to gain better understanding of certain structural factors that could influence the catalytic performance.

25 ENERGY STORAGE↗
DOE OSTI2023

Mixed nitrate and metal contamination influences operational speciation of toxic and essential elements

Environmental contamination constrains microbial communities impacting diversity and total metabolic activity. The former S-3 Ponds contamination site at Oak Ridge Reservation (ORR), TN, has elevated concentrations of nitric acid and multiple metals from decades of processing nuclear material. To determine the nature of the metal contamination in the sediment, a three-step sequential chemical extraction (BCR) was performed on sediment segments from a core located upgradient (EB271, non-contaminated) and one downgradient (EB106, contaminated) of the S-3 Ponds. The resulting exchangeable, reducing, and oxidizing fractions were analyzed for 18 different elements. Comparison of the two cores revealed changes in operational speciation for several elements caused by the contamination. Those present from the S-3 Ponds, including Al, U, Co, Cu, Ni, and Cd, were not only elevated in concentration in the EB106 core but were also operationally more available with increased mobility in the acidic environment. Other elements, including Mg, Ca, P, V, As, and Mo, were less operationally available in EB106 having decreased concentrations in the exchangeable fraction. Here, the bioavailability of essential macro nutrients Mg, Ca, and P from the two types of sediment was determined using three metal-tolerant bacteria previously isolated from ORR. Mg and Ca were available from both sediments for all three strains; however, P was not bioavailable from either sediment for any strain. The decreased operational speciation of P in contaminated ORR sediment may increase the dependence of the microbial community on other pools of P or select for microorganisms with increased P scavenging capabilities. Hence, the microbial community at the former S-3 Ponds contamination site may be constrained not only by increased toxic metal concentrations but also by the availability of essential elements, including P.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Ecological connectivity and in-kind mitigation in a regulatory decision framework: A case study with an amphibian habitat specialist

Ecological connectivity is critical to the survival and long-term viability of populations but is often overlooked in regulatory frameworks. We integrated landscape-level processes into a mitigation strategy for impacts to aquatic resources on the U.S. Department of Energy (DOE) Oak Ridge Reservation (ORR) in eastern Tennessee. Wetlands on the ORR, which contain significant breeding populations of the imperiled four-toed salamander (Hemidactylium scutatum) and tubercled rein orchid (Platanthera flava var. herbiola), will be impacted by construction of an environmental waste disposal facility under the Comprehensive Environmental Response, Compensation, and Liability Act of 1980 (CERCLA). Here, we used a modified Kepner-Tregoe decision analysis to select general mitigation options that balanced regulatory requirements and interest group perspectives. We emphasized habitat connectivity through models that prioritized an area's importance to natural area connectivity (centrality) and maintenance of population structure for an affected habitat specialist (four-toed salamanders). We also emphasized in-kind mitigation through the preservation and enhancement of ecologically similar resources and the translocation and establishment of a new subpopulation of four-toed salamanders elsewhere on the ORR. We ultimately released over 500 juvenile salamanders that originated from the impacted site into the chosen mitigation wetlands. By doing so under the constraints of a time-sensitive CERCLA remediation effort and exceeding its substantive requirements, this work underscores feasibility. Ecological connectivity and the conservation of species that are not afforded explicit regulatory processes can be effectively and efficiently integrated into environmental decision-making and land use planning.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

The effect of water vapor on surface oxygen exchange kinetics of thin film (La,Sr)(Co,Fe)O 3-δ

Oxygen reduction and transport in electrochemical applications are strongly affected by the reactant gas composition, including impurities such as water. Understanding the relationship between oxygen reactivity and humidity is key for attaining stability and high efficiency of solid oxide fuel cells, which are especially attractive for transportation applications as low emission power generation devices. Both short- and long-term effects of moisture have previously been associated with use of ambient air. To better understand these effects, we study oxygen exchange kinetics at the cathode surface and the cathode/electrolyte interface using La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ (LSCF) epitaxial thin films as a model-surface system. In situ synchrotron X-ray techniques evaluate the oxygen reduction reaction (ORR) kinetics in response to environmental variables. The results suggest a clear enhancement of the ORR rate upon short term exposure of the perovskite-structured films to water. Finally, on the basis of these measurements, along with in situ X-ray characterization of Sr segregation and computational first-principles studies, we suggest a model for this increased ORR activity that may lead to further improvements by stabilizing active cathode surface configurations.

25 ENERGY STORAGE↗
DOE OSTI2026

Hierarchical low Pt-loading “core-shell” electrocatalysts for the oxygen reduction reaction in fuel cells

The sluggish kinetics of the oxygen reduction reaction (ORR) hinder cost-effective polymer electrolyte fuel cells (PEFCs), which rely on scarce, expensive platinum-based electrocatalysts (ECs). Here, we present a novel synthesis method for ORR ECs achieving exceptional platinum utilization. The design features a hierarchical “multi-carbon” support comprising carbon nanoparticles interacting with graphene nanoplatelets as the “core”, encapsulated by a porous carbon nitride (CN) “shell”. This configuration promotes strong core/shell interactions and a bimodal active site distribution, consisting of chemically dispersed Pt and Ni single-atom complexes and PtNix alloy nanoclusters embedded in the CN shell. These advantages enable high activity and durability, achieving an ORR activity of 1.6 A mgPt−1 at 0.9 V vs. RHE-an order of magnitude higher than Pt/C (0.17 A mgPt−1). A proof-of-concept PEFC demonstrates a specific power of 12.0 kW gPt−1 at 0.60 V. This approach offers a significant step toward more efficient and sustainable PEFC technologies.

Pagot, Gioele [University of Padova, Italy]↗
DOE OSTI2020

Tailoring a Three-Phase Microenvironment for High-Performance Oxygen Reduction Reaction in Proton Exchange Membrane Fuel Cells

Despite tremendous progress in catalyst development for rate-limiting cathodic oxygen reduction reaction (ORR), reducing Pt usage while meeting performance requirements in practical proton exchange membrane fuel cells (PEMFCs) remains a challenge. The ORR in PEMFCs occurs at a catalyst–electrolyte–gas three-phase interface. A desirable interface should exhibit highly active and available catalytic sites, as well as allow efficient oxygen and proton feeding to the catalytic sites and timely removal of water to avoid interface flooding. In this work, we report the design of a three-phase microenvironment in PEFMCs, showing that carbon surface chemistry can be tuned to modulate its interaction with the ionomers and create favorable transport paths for rapid delivery of both reactants and products. With such an elaborate interfacial design, for the first time we have demonstrated PEMFCs with all key ORR catalyst performance metrics, including mass activity, rated power, and durability, surpassing the US Department of Energy targets.

25 ENERGY STORAGE↗
DOE OSTI2021

Boosting the activity of non-platinum group metal electrocatalyst for the reduction of oxygen via dual-ligated atomically dispersed precursors immobilized on carbon supports

This paper describes the use of both atomically dispersed precursors (ADPs) and conductive carbon dispersion towards the synthesis of iron-based single atom electrocatalysts for the oxygen reduction reaction (ORR). For non-platinum group metal (non-PGM) catalysts, single iron, cobalt or manganese atoms coordinated with nitrogen are the most active structures towards the ORR. Achieving a high density of active sites made of single atoms is still challenging, requiring careful controls of pyrolysis to reduce the sintering of metal active sites. Herewith, we present a new strategy to synthesize iron-based single atom ORR electrocatalysts using a two pronged approach. We first designed a dual-ligated metal organic framework (MOF) precursor. This MOF was then immobilized onto Ketjen black carbon that serves as a conductive dispersion medium for creating the highly dispersed single atom sites. In this work, we demonstrate a near complete dispersion of the iron sites without obvious formation of nanoparticles. The activity of the resulting electrocatalyst exhibited an onset potential of 0.96 V and a half-wave potential of 0.84 V vs. reversible hydrogen electrode (RHE).

42 ENGINEERING↗
DOE OSTI2024

Graphene-supported single atom catalysts for high performance lithium-oxygen batteries

The optimal choice of d-block metals in single atom catalysts (SACs) is crucial for designing efficient electrocatalysts for activating the Oxygen reduction reaction (ORR)/ Oxygen evolution reaction (OER) in lithiumoxygen batteries (LOBs). Herein, we used the Quantum Mechanics methods to understand the origin of reactivity for a series of 16 d-block metals supported on nitrogen-doped graphene as SACs for ORR and OER in LOBs. Based on the Gibbs free energy calculations, we found that among the 16 SACs investigated, Zn-SAC exhibits the highest electrochemical activity with the lowest overpotential of 0.17 V. Here we then used machine learning (ML) to develop an intrinsic descriptor, phi, that correlates the catalytic activity with electronic and chemical properties of the catalytic centers at the M-N 4 active site on graphene surface. We established a linear relationship between phi and the catalytic activity that provides guidance for designing efficient SACs for electrocatalysis in LOBs. To validate these predictions, we report electrochemical measurements showing that Zn-SAC exhibits an ultra-stable cyclability with reduced overpotentials over Mo-SAC and nitrogen-doped graphene (NG), confirming our theoretical prediction. This fundamental work provides a deep understanding on the rational design of efficient SACs for OER/ ORR in LOBs.

25 ENERGY STORAGE↗
DOE OSTI2020

Developing Scaling Relationships for Molecular Electrocatalysis through Studies of Fe-Porphyrin-Catalyzed O 2 Reduction

The oxygen reduction reaction (ORR) is a multiproton/multielectron transformation in which dioxygen (O 2 ) is reduced to water or hydrogen peroxide and serves as the cathode reaction in most fuel cells. The ORR (O 2 + 4e – + 4H + → 2H 2 O) involves up to nine substrates and thus requires navigating a complicated reaction landscape, typically with several high-energy intermediates. Many catalysts can perform this reaction, though few operate with fast rates and at low overpotentials (close to the thermodynamic potential). Attempts to optimize these parameters, both in homogeneous and heterogeneous electrocatalytic systems, have focused on modifying catalyst design and understanding kinetic/thermodynamic relationships between catalytic intermediates. One such method for analyzing and predicting catalyst reactivity and efficiency has been the development of “molecular scaling relationships”. In this work, we share our experience deriving and utilizing molecular scaling relationships for soluble, iron-porphyrin-catalyzed O 2 reduction in organic solvents. These relationships correlate turnover frequencies (TOF max ) and effective overpotentials (η eff ), properties uniquely defined for homogeneous catalysts. Following a general introduction of scaling relationships for both homogeneous and heterogeneous electrocatalysis, we describe the components of such scaling relationships: (i) the overall thermochemistry of the reaction and (ii) the rate and rate law of the catalyzed reaction. We then show how connecting these thermodynamic and kinetic parameters reveals multiple molecular scaling relationships for iron-porphyrin-catalyzed O 2 reduction. For example, the log(TOF max ) responds steeply to changes in ηeff that result from different catalyst reduction potentials (18.5 decades in TOF max /V in η eff ) but much less dramatically to changes in η eff that arise from varying the pKa of the acid buffer (5.1 decades in TOF max /V in η eff ). Thus, a single scaling relationship is not always sufficient for describing molecular electrocatalysis. This is particularly evident when the catalyst identity and reaction conditions are coupled. Using these multiple scaling relationships, we demonstrate that the metrics of turnover frequency and effective overpotential can be predictably tuned to achieve faster rates at lowered overpotentials. This Account uses a collection of related stories describing our research on soluble iron-porphyrin-catalyzed ORR to show how molecular scaling relationships can be derived and used for any electrocatalytic reaction. Such scaling relationships are powerful tools that connect the thermochemistry, mechanism, and rate law for a catalytic system. We hope that this collection shows the utility and simplicity of the molecular scaling approach for understanding catalysis, for enabling direct comparisons between catalyst systems, and for optimizing catalytic processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗