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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 163 records · Page 9

Monovalent ion–graphene oxide interactions are controlled by carboxylic acid groups: Sum frequency generation spectroscopy studies

Graphene oxide (GO) is a two-dimensional, mechanically strong, and chemically tunable material for separations. Elucidating GO–ion–water interactions at the molecular scale is highly important for predictive understanding of separation systems. However, direct observations of the nanometer region by GO surfaces under operando conditions are not trivial. Therefore, thin films of GO at the air/water interface can be used as model systems. With this approach, we study the effects of alkali metal ions on water organization near graphene oxide films at the air/water interface using vibrational sum frequency generation (SFG) spectroscopy. Here, we also use an arachidic acid Langmuir monolayer as a benchmark for a pure carboxylic acid surface. Theoretical modeling of the concentration-dependent sum frequency signal from graphene oxide and arachidic acid surfaces reveals that the adsorption of monovalent ions is mainly controlled by the carboxylic acid groups on graphene oxide. An in-depth analysis of sum frequency spectra reveals at least three distinct water populations with different hydrogen bonding strengths. The origin of each population can be identified from concentration dependent variations of their SFG signal. Interestingly, an interfacial water structure seemed mostly insensitive to the character of the alkali cation, in contrast to similar studies conducted at the silica/water interface. However, we observed an ion-specific effect with lithium, whose strong hydration prevented direct interactions with the graphene oxide film.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

White Dwarf Binaries across the H-R Diagram

We created the APOGEE-GALEX-Gaia catalog to study white dwarf (WD) binaries. This database aims to create a minimally biased sample of WD binary systems identified from a combination of GALEX, Gaia, and APOGEE data to increase the number of WD binaries with orbital parameters and chemical compositions. We identify 3414 sources as WD binary candidates, with nondegenerate companions of spectral types between F and M, including main-sequence stars, main-sequence binaries, subgiants, sub-subgiants, red giants, and red clump stars. Among our findings are (a) a total of 1806 systems having inferred WD radii R < 25 R ⊕ , which constitute a more reliable group of WD binary candidates within the main sample; (b) a difference in the metallicity distribution function between WD binary candidates and the control sample of most luminous giants (M H < -3.0); (c) the existence of a population of sub-subgiants with WD companions; (d) evidence for shorter periods in binaries that contain WDs compared to those that do not, as shown by the cumulative distributions of APOGEE radial velocity shifts; (e) evidence for systemic orbital evolution in a sample of 252 WD binaries with orbital periods, based on differences in the period distribution between systems with red clump, main-sequence binary, and sub-subgiant companions and systems with main-sequence or red giant companions; and (f) evidence for chemical enrichment during common envelope (CE) evolution, shown by lower metallicities in wide WD binary candidates (P > 100 days) compared to post-CE (P < 100 days) WD binary candidates.

79 ASTRONOMY AND ASTROPHYSICS↗

Direct Observation of Morphological and Chemical Changes during the Oxidation of Model Inorganic Ligand-Capped Particles

Functionalization and volatilization are competing reactions during the oxidation of carbonaceous materials and are important processes in many different areas of science and technology. Here, we present a combined ambient pressure X-ray photoelectron spectroscopy (APXPS) and grazing incidence X-ray scattering (GIXS) investigation of the oxidation of oleic acid ligands surrounding NaYF 4 nanoparticles (NPs) deposited onto SiO x /Si substrates. While APXPS monitors the evolution of the oxidation products, GIXS provides insight into the morphology of the ligands and particles before and after the oxidation. Our investigation shows that the oxidation of the oleic acid ligands proceeds at O 2 partial pressures of below 1 mbar in the presence of X-rays, with the oxidation eventually reaching a steady state in which mainly CH x and –COOH functional groups are observed. The scattering data reveal that the oxidation and volatilization reaction proceeds preferentially on the side of the particle facing the gas phase, leading to the formation of a chemically and morphologically asymmetric ligand layer. This comprehensive picture of the oxidation process could be obtained only by combining the X-ray scattering and APXPS data. The investigation presented here lays the foundation for further studies of the stability of NP layers in the presence of reactive trace gases and ionizing radiation and for other nanoscale systems where chemical and morphological changes happen simultaneously and cannot be understood in isolation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Statistical estimates of the binary properties of rotational variables

ABSTRACT We present a model to estimate the average primary masses, companion mass ranges, the inclination limit for recognizing a rotational variable, and the primary mass spreads for populations of binary stars. The model fits a population’s binary mass function distribution and allows for a probability that some mass functions are incorrectly estimated. Using tests with synthetic data, we assess the model’s sensitivity to each parameter, finding that we are most sensitive to the average primary mass and the minimum companion mass, with less sensitivity to the inclination limit and little to no sensitivity to the primary mass spread. We apply the model to five populations of binary spotted rotational variables identified in ASAS-SN, computing their binary mass functions using RV data from APOGEE. Their average primary mass estimates are consistent with our expectations based on their CMD locations ($\sim 0.75 \, {\rm M}_{\odot }$ for lower main sequence primaries and $\sim 0.9$–$1.2 \, {\rm M}_{\odot }$ for RS CVn and sub-subgiants). Their companion mass range estimates allow companion masses down to $M_2/M_1\simeq 0.1$, although the main sequence population may have a higher minimum mass fraction ($\sim 0.4$). We see weak evidence of an inclination limit $\gtrsim 50^{\circ }$ for the main sequence and sub-subgiant groups and no evidence of an inclination limit in the other groups. No groups show strong evidence for a preferred primary mass spread. We conclude by demonstrating that the approach will provide significantly better estimates of the primary mass and the minimum mass ratio and reasonable sensitivity to the inclination limit with 10 times as many systems.

Phillips, Anya (ORCID:000900051914974X)↗

Perspectives on UV and x-ray photoelectron spectroscopy

Atomic photoionization using electron spectroscopy was one of the scientific topics in which Professor David A. Shirley excelled and established a research legacy. We discuss selected highlights of atomic photoionization research done by the Shirley group beginning in the 1970s. Our main topics are electron correlation satellites, photoelectron angular distributions with tunable synchrotron radiation, and developments of theory. We also discuss examples of more recent research that extends the earlier work, including double K-shell photoionization, nondipole interactions, and the pervasive role of interchannel coupling. Furthermore, we conclude with examples of current experimental and theoretical research.

74 ATOMIC AND MOLECULAR PHYSICS↗

High Flux Isotope Reactor Uncertainty Factors

This report provides a brief summary of the uncertainty factors used for High Flux Isotope Reactor (HFIR) steady-state heat transfer analyses. These factors are mainly used in the HFIR Steady-State Heat Transfer Code (HSSHTC) to perform core thermal margin evaluations that determine safe reactor operation. The attempt to classify these factors stems from the assumption that the current approach is characterized by an excess of conservatism, thereby restricting reactor performance. The work documented herein was of a limited scope and pertained mainly to factors’ description and initial grouping based on their functional use. Suggestions are provided for further evaluation for the low-enriched uranium (LEU) to the uranium silicide dispersion fuel (U 3 Si 2 -Al).

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

One fold, many functions—M23 family of peptidoglycan hydrolases

Bacterial cell walls are the guards of cell integrity. They are composed of peptidoglycan that provides rigidity to sustain internal turgor and ensures isolation from the external environment. In addition, they harbor the enzymatic machinery to secure cell wall modulations needed throughout the bacterial lifespan. The main players in this process are peptidoglycan hydrolases, a large group of enzymes with diverse specificities and different mechanisms of action. They are commonly, but not exclusively, found in prokaryotes. Although in most cases, these enzymes share the same molecular function, namely peptidoglycan hydrolysis, they are leveraged to perform a variety of physiological roles. A well-investigated family of peptidoglycan hydrolases is M23 peptidases, which display a very conserved fold, but their spectrum of lytic action is broad and includes both Gram- positive and Gram- negative bacteria. In this review, we summarize the structural, biochemical, and functional studies concerning the M23 family of peptidases based on literature and complement this knowledge by performing large-scale analyses of available protein sequences. This review has led us to gain new insight into the role of surface charge in the activity of this group of enzymes. We present relevant conclusions drawn from the analysis of available structures and indicate the main structural features that play a crucial role in specificity determination and mechanisms of latency. Our work systematizes the knowledge of the M23 family enzymes in the context of their unique antimicrobial potential against drug-resistant pathogens and presents possibilities to modulate and engineer their features to develop perfect antibacterial weapons.

Razew, Alicja↗

Experimental protocol for phase 1 of the APARC QUOCA (QUasibiennial oscillation and Ozone Chemistry interactions in the Atmosphere) working group

The quasi-biennial oscillation (QBO) is the main mode of variability in the tropical stratosphere, influencing the predictability of other regions in the atmosphere through its teleconnections to the stratospheric polar vortices and coupling to surface tropical and extratropical variability. However, climate and forecasting models consistently underestimate QBO amplitudes in the lower stratosphere, likely contributing to their failure to simulate these teleconnections. One underexplored contributor to model biases is missing representation of ozone-radiative feedbacks, which enhance temperature variability in the lower stratosphere, particularly at periods at and greater than the QBO (>28 months). While previous studies suggest that ozone-radiative feedbacks can impact QBO periods, amplitudes and the associated secondary circulation in the lower stratosphere, the reported impacts differ widely among models and are hard to interpret due to differences in methodology. To this end, here we propose a coordinated experimental protocol – held joint between the Atmospheric Processes and their Role in Climate (APARC) Quasi-Biennial Oscillation Initiative (QBOi) and Chemistry Climate Modeling Initiative (CCMI) activities – which is aimed at assessing the coupling between stratospheric ozone, temperature and the circulation. We use the proposed experiments to define the ozone feedback on the QBO in both present-day and idealized (abrupt quadrupling of carbon dioxide) climates. While primary focus is on the QBO, the proposed protocol also enables analysis of other aspects of ozone-radiative-dynamical coupling in the atmosphere, including impacts on the Brewer-Dobson Circulation and tropospheric eddy-driven jet responses to future climate change. Here we document the scientific rationale and design of the QUOCA Phase 1 experiments, summarize the data request, and give a brief overview of participating models. Preliminary results using the NASA Goddard Institute for Space Studies E2-2 climate model are used to illustrate sensitivities to certain methodological choices.

Environmental sciences↗

Achieving High Permittivity Paraelectric Behavior in Mesogen-Free Sulfonylated Chiral Polyethers with Smectic C Liquid Crystalline Self-Assembly

Ferroelectric liquid crystalline polymers (LCPs) with a high spontaneous polarization (P s ) are of great interest for the fabrication of advanced electronic devices. However, conventional ferroelectric LCPs typically exhibit low spontaneous polarization, only around 1 mC/m 2 . To increase the orientational polarization for ferroelectric LCPs, in this work, we designed mesogen-free comb-shaped LCPs based on isotactic polyepichlorohydrin, which contained highly dipolar sulfonyl groups (dipole moment of 4.5 Debye) in the side chains. The goal was to increase dipole density and induce ferroelectric switching. In this new series of mesogen-free LCPs, the sulfonyl groups were first moved away from the main chain to mitigate strong dipole–dipole interactions. Second, methyl-branched alkyl side chains were implemented to decrease the crystallizability and induce the Smectic C (SmC) self-assembly. Intriguingly, these SmC samples, for the first time, exhibited typical paraelectric behavior (i.e., slim S-shaped single hysteresis loops) with a high dielectric constant in the range of 20–30. Finally, learning from the knowledge obtained from this study, we will be able to design new mesogen-free LCPs with tailor-made dipole–dipole interactions and realize ferroelectricity.

36 MATERIALS SCIENCE↗

Heat Transfer in Nuclear Waste Glasses: Measurements and Modeling of Thermal Radiation Properties

We measured and modeled near infrared extinction of nuclear waste glasses from 300 °C to 1150 °C to enable predictive radiation heat transfer and thermal conductivity estimates. A composition and redox informed model resolved contributions from key chromophores (Fe+2-O-Fe+3, V+4, free and bonded ?Si-OH groups) and, when present, spinel particles that can cause strong scattering. The model reproduced measured absorption from room temperature up to 1150 °C, with minor discrepancies near 1 µm (likely due to possible trace impurities) and 2.5 µm (linked to uncertainty in hydroxy groups). Spectra showed silicate melts were semitransparent mainly in the 0.5–4.0 µm window, responsible for radiation thermal conductivity that generally increases with increasing temperature. We quantified the dependence of effective thermal conductivity on dissolved water and provided distributions across >100 LAW/HLW/DFHLW melts at 1150 °C, supporting improved melter heat transfer modeling.

Ferkl, Pavel↗

Tuning the reactivity of carbon surfaces with oxygen-containing functional groups

Oxygen-containing carbons are promising supports and metal-free catalysts for many reactions. However, distinguishing the role of various oxygen functional groups and quantifying and tuning each functionality is still difficult. Here we investigate the role of Brønsted acidic oxygen-containing functional groups by synthesizing a diverse library of materials. By combining acid-catalyzed elimination probe chemistry, comprehensive surface characterizations, 15N isotopically labeled acetonitrile adsorption coupled with magic-angle spinning nuclear magnetic resonance, machine learning, and density-functional theory calculations, we demonstrate that phenolic is the main acid site in gas-phase chemistries and unexpectedly carboxylic groups are much less acidic than phenolic groups in the graphitized mesoporous carbon due to electron density delocalization induced by the aromatic rings of graphitic carbon. The methodology can identify acidic sites in oxygenated carbon materials in solid acid catalyst-driven chemistry.

Zhou, Jiahua↗

Landscape responses to intraplate deformation in the Kalahari constrained by sediment provenance and chronology in the Okavango Basin

The structural depression that occupies the Okavango Basin in southern Africa comprises a depo-centre within the intracratonic Kalahari Basin where sediments of the Cenozoic Kalahari Group have accumulated. The Okavango Basin has been formed due to stretching and subsidence at an area of diffused deformation, southwestwards to the main East African Rift System (EARS). Sediments from two full Kalahari Group sequences, located on opposite sides of the Gumare Fault that forms a major fault within the Okavango Basin, were studied to determine their provenance and chronology. Terrestrial Cosmogenic Nuclide (TCN) 26 Al/ 10 Be burial dating was used to constrain a chronostratigraphical framework, and Pb, Sr, and Nd isotopic ratios combined with geochemical and sedimentological analyses were applied to track the source areas of the sediments.Results indicate the following sequence of basin filling: (a) Accumulation between ca. 4–3 Ma during which the currently downthrown (southern) block received a mixture of sediments mostly from the Choma-Kalomo, Ghanzi-Chobe, and Damara terranes, and possibly from the Lufilian Belt and/or Karoo basalts during earlier stages of deposition. Simultaneously, the upthrown (northern) block received sediments from more distant Archean sources in the Zimbabwe and/or Kasai cratons, (b) Hiatus in sedimentation occurred at both sites between ca. 3–2 Ma, (c) Sediments on both sides of the Gumare Fault share a similar source (Angolan Shield) with minor distinct contributions to the downthrown block from the Kasai Craton and local sources input to the upthrown block, and (d) Regional distribution of aeolian sand since at least 1 Ma. The change in source areas is attributed to rearrangements of the drainage systems that were probably linked to vertical crustal movements on the margins of the Okavango Basin. The tectonically induced morphodynamics controlled the landscape evolution of the endorheic basin where vast lakes, wetlands and salt pans have developed through time.

58 GEOSCIENCES↗

Particle Swarm Optimisation for group structure optimization for radiotherapy shielding

Neutron transport simulations are ubiquitous in nuclear engineering because they allow one to model experimental systems and render a model platform for easy perturbation of experimental designs. In addition, simulations allow one to gain experimental insight without actually having to go through the trouble of building a physical experiment. Neutron transport simulations can be stochastic or deterministic based. Stochastic neutron transport simulations are typically simulated using the Monte Carlo method and yield very accurate solutions but are computationally expensive, while deterministic methods are typically faster but can be less accurate. Here we focus on optimizing the accuracy of deterministic neutron transport simulations for radiotherapy simulations. Deterministic neutron transport requires discretization of angle, energy, and space to appropriately analyze the system one is trying to model. Discretization of energy is challenging because of the highly variable neutron flux at certain neutron energies. Improper discretization of energy in the transport model can lead to erroneous results and therefore inaccurate interpretations of the solution. In this study, we evaluate Particle Swarm Optimization (PSO) as a mechanism for selecting optimal group structures for radiotherapy shielding. We tested the particle swarm optimization algorithm on radiotherapy shielding problems using Los Alamos National Laboratory's (LANL) main deterministic transport code PARTISN. Results show that the optimized energy group structures generated from the optimization algorithm outperformed LANL's standard energy group structures, and therefore demonstrate utility in using PSO to expedite computation times due to the increased accuracy obtained with a smaller but optimized group structure. (authors)

43 PARTICLE ACCELERATORS↗

An isotopic labeling investigation into the influence of the nitro group on LLM-105 thermal decomposition

Here, this work presents the first application of isotopically labeled LLM-105 (2,6-diamino-3,5-dinitropyrazine-1-oxide) to investigate thermal decomposition pathways. Specially synthesized LLM-105 isotopologues were utilized to isolate the influence of labeled 15 NO 2 nitro groups on the formation of lightgas products. Simultaneous differential scanning calorimetry, thermo-gravimetric, and mass spectrometry measurements were employed to track the evolution of product gases, enabling the direct comparison of isotopically shifted species with unlabeled LLM-105. Key findings show that C 2 N 2 production is mainly dependent on nitrogen sources from either the amine groups or the pyrazine ring (i.e., not the nitro groups). The formation of NO, N 2 , and N 2 O all involves the nitro groups to some extent. NO (nitric oxide) was found to be the predominant gas species directly formed from the nitro group of LLM-105. In contrast, mixed nitrogen isotopologues of N 2 and N 2 O (i.e., 14 N 15 N and 15 NNO) formed more readily in comparison to their pure counterparts (i.e., 15 N 2 and 15 N 2 O). This indicates the amine and/or pyrazine groups of LLM-105, in addition to the nitro group, are involved in the decomposition pathways forming N 2 and N 2 O. In addition, our investigation led to the discovery of two previously unreported decomposition products (CHO and HNCO), which were confirmed through hydrogen labelling utilizing deuterium isotopes. These results provide detailed speciation trends of gaseous products during LLM-105 decomposition, offering new insights into reaction pathways. Experimental data reported here will support the development of a detailed chemical kinetics model for LLM-105, essential for the safe handling of high explosives.

Chemistry - Chemical explosives↗

Choosing the Best Modeling Platform for Radiological Risk Assessment Models - 20468

Radiological risk assessments, in the form of performance or safety assessments, are often required under regulations or guidance for remediation of contaminated land, decommissioning of contaminated buildings or structures, and radioactive waste disposal. These risk assessments are usually supported by fate and transport models that address decay and ingrowth of radionuclides, as well as their movement through engineered systems and the natural environment. These models are often projected thousands, or more, years into the future, largely because the radioactive species change through decay and ingrowth, and hence the magnitude of the radioactive effect changes with time. There are many computer codes that are available to address this type of modeling. They range from addressing specific pathways or processes such as infiltration of water, groundwater, surface water, air, biota, diffusion and advection of water and gases, to those that try to couple all processes together to evaluate the impact of fate and transport through the entire system to places in space and time to which access is assumed. These different types of codes are sometimes separated with the monikers process-level and systems-level codes, although it is often not clear that this separation does justice to the capabilities of the many codes that are available to evaluate fate and transport of radionuclides. The focus of this paper is the latter group of modeling codes. Several systems level modeling codes exist and are used. There are differences between these codes in terms of utility, flexibility, complexity and cost. The purpose of this paper is to compare a few of these codes in the context of work currently being performed by the International Atomic Energy Agency (IAEA) Modeling and Data for Radiological Impact Assessments (MODARIA) II Working Group 1 (WG1). The MODARIA II WG1's main focus is how stakeholder engaged decision analysis can, or should, be applied to radiological contamination problems so that better, longstanding, sustainable, solutions are reached. However, the WG1 also recognizes the potential impact of the modeling tools that are chosen to address radiological risk, which is often a primary objective of decision making for radiological problems. Other objectives might also be important, such as constraining costs, obtaining financing, minimizing impact on ecosystems, saving cultural resources, saving jobs, farmland, environmental justice, etc., in a full decision analysis for a given radiological contamination problem, but none of these other objectives have the same types of complex modeling needs as minimize radiological dose. Consequently, a further focus of WG1 is to evaluate the potential impacts on decision making of the choice of fate and transport, and risk assessment, modeling codes that are used to support decision making. The WG1 will produce a report at the end of 2020 that will focus on an approach to effective decision making and stakeholder engagement. The report will also consider the role that performance assessment modeling should play in the decision-making process, including the impact of the choice of modeling tools or computer codes on risk-informed decision making. Several sites around the World have been made available by Member States for these model comparisons, and several modeling tools have been considered. However, the focus of this paper is on two of the sites, one in Belgium and one in Ukraine, and on three of the tools: NORMALYSA (NORM And Legacy Site Assessment); GoldSim{sup C}, and AMBER{sup C}. The final report from this working group will also cover other modeling tools, including RESRAD, and PC-Cream{sup R}. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

AP-XPS Study of the Reaction of O 2 and CO 2 with Zn–Au(111) Surface Alloys: Activation of O–O/C–O Bonds and the Formation of ZnO

Synchrotron-based ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) was used to study the dissociation of O 2 and CO 2 on Zn-Au(111) alloys which contained 0.2-0.3 monolayers of zinc. Although Au(111) is inert, the alloys displayed a high activity for the cleavages of O-O and C-O bonds at room temperature with the formation of ZnO x species. Dissociative adsorption of O 2 at 300 K destroyed the alloys and the results of AP-XPS pointed to the co-existence of two types of oxygen species on the surface: ZnO x and chemisorbed O atoms (O chem ) on Au or the Au-ZnO interface. Annealing from room temperature to 600 K induced a O chem → ZnO x transformation that reflected the poor stability of O atoms on Au(111). The Zn-Au(111) systems exhibited a reactivity towards CO 2 that was much larger than that seen for Au(111), Cu(111) or surfaces of late transition metals like, Ni, Pd or Pt. At 300 K, CO 2 underwent partial dissociation depositing large amounts of O chem on the surface with minor formation of ZnO x . In addition, the deposited O chem reacted with CO 2 to form surface carbonate groups. Dosing of CO 2 at 500-600 K mainly led to the formation of ZnO x and the surface carbonate almost disappeared. In the presence of hydrogen, i.e. reaction feeds with a CO 2 to H 2 ratio of 1:3, the surface chemistry at 300 K was very similar to that seen for pure CO 2 with the formation of ZnO x and carbonate groups. In contrast, at 500-600 K, reaction with hydrogen induced the removal of ZnO x and CO 3 /HCOO species. Finally, our AP-XPS results are consistent with the idea that CO 2 hydrogenation on AuZn alloys involves a redox process where there is sequential oxidation by CO 2 and reduction by H 2 to yield methanol.

36 MATERIALS SCIENCE↗

Smectic C Self‐Assembly in Mesogen‐Free Liquid Crystalline Chiral Polyethers with Sulfonylated Methyl‐Branched Side Chains

Abstract To realize advanced electrical applications for ferroelectric liquid crystalline polymers, high spontaneous polarization ( P s ) is highly desired. However, current ferroelectric liquid crystalline polymers usually exhibit a low P s . In this work, mesogen‐free, chiral polyethers containing sulfonylated methyl‐branched alkyl side chains with a (CH 2 ) 3 O spacer between the sulfonyl and the branched alkyl groups are designed and synthesized. In contrast to the linear n ‐alkyl side chains, the methyl‐branched alkyl side chains induce chain tilting in the smectic layers. When double chirality exists in both the main chain and the side chains, a crystalline structure is observed after mechanical stretching. Intriguingly, when single chirality exists in either the backbone or the side chains, a liquid crystalline smectic C phase is obtained. The electric displacement–electric field study, however, does not show typical ferroelectric switching, although the dielectric constants are relatively high for these liquid crystalline polymers. This is likely because the dipole–dipole interactions among neighboring sulfonyl groups along the main chain are so strong that the ferroelectric switching is hindered in the samples. For the future work, it is desired to weaken the dipole–dipole interaction to achieve ferroelectricity in these mesogen‐free liquid crystalline polymers.

36 MATERIALS SCIENCE↗

Performance enhancement and degradation mechanism identification of a single-atom Co–N–C catalyst for proton exchange membrane fuel cells

Development of platinum group metal (PGM)-free catalysts for oxygen reduction reaction (ORR) has been a strategic research topic for proton exchange membrane (PEM) fuel cells. Present state-of-art PGM-free ORR catalysts are Fe, N co-doped carbon (Fe-N-C) catalysts, which unfortunately exhibit instability concerns. Herein, we report a stable atomically dispersed Co, N co-doped carbon (Co-N-C) catalyst with high Co content of 1.0 at% and the active site, i.e., the coordination of Co, is CoN2+2 in nature. The Co-N-C catalyst demonstrated high ORR activity comparable to, and high stability over 3 times better than, that of the Fe-N-C catalyst. It also achieved a high activity of 22 mA cm2 at 0.9 ViR-free and a power density of 0.61 W cm-2 under 1.0 bar H2/O2. Further, we identify two main degradation mechanisms of the PGM-free catalysts: catalyst oxidation by H2O2/radicals and demetalation. The improved stability of Co-N-C relative to Fe-N-C is attributed to less Fenton-reactive nature of Co and significantly enhanced resistance to demetalation of Co-N-C.

Xie, Xiaohong↗