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At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Single Atomic Iron Site Catalysts via Benign Aqueous Synthesis for Durability Improvement in Proton Exchange Membrane Fuel Cells

Atomically-dispersed iron-nitrogen-carbon (Fe–N–C) catalysts have arisen as promising candidates for replacing the costly precious metal catalysts in fuel cells but still face some grand challenges, such as insufficient site density and durability. Herein, we report a self-assembly method in an aqueous solution to develop an atomically-dispersed iron catalyst with high oxygen reduction reaction (ORR) activity and stability in acidic electrolytes. As determined by high-resolution transmission electron microscopy (HR-TEM), X-ray absorption spectroscopy (XAS), and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), this benign aqueous synthesis strategy facilitates the formation of homogeneous atomic nitrogen-coordinated iron sites embedded in a popcorn-like porous graphitic carbon matrix. These catalyst properties contribute to the improved ORR kinetic current density and mass transport. By controlling synthesis chemistry, the correlation between structure and property is systematically investigated. In this work, the iron content is the most critical material property and can regulate site density and graphitic carbon structures in the catalyst, impacting catalytic activity and stability. The enhanced performance and durability were examined in both acidic aqueous electrolytes and membrane electrode assemblies.

25 ENERGY STORAGE↗
NASA NTRS1992

Pregraphitic and poorly graphitised carbons in porous chondritic micrometeorites

Two forms of crystalline carbon in porous chondritic micrometeorites W7029E5, U2011C2, and U2022C7/C8 are mixed layered pregraphitic carbons with C/(C+H+O+N) (at. pct) about 0.45. This bulk composition is inferred from the presence of three groupings of d(002) basal spacings at 0.45 nm, 0.37 nm, and 0.348 nm. Mixed layered carbons represent incomplete carbonization and graphitization of precursor material. In U2022C7/C8, carbonization mostly involved volatile loss. The formation of pregraphitic carbons indicates a sustained thermal regime in parent bodies of these micrometeorities (i.e., short-period comets, outer-belt asteroids, or protocomet nuclei). Temperatures of the sustained thermal regime remain unspecified, but carbon reactions were probably facilitated by catalytic support from layer silicates in these samples. Poorly graphitized carbon in U2022C7/C8 formed during a transient thermal event which is most likely flash-heating during micrometeoroid deceleration in the earth's atmosphere.

Rietmeijer, Frans J. M.↗
NASA NTRS2002

Carbon Nanotubes Growth by CVD on Graphite Fibers

Due to the superior electrical and mechanical properties of carbon nanotubes (CNT), synthesizing CNT on various substances for electronics devices and reinforced composites have been engaged in many efforts for applications. This presentation will illustrate CNT synthesized on graphite fibers by thermal CVD. On the fiber surface, iron nanoparticles as catalysts for CNT growth are coated. The growth temperature ranges from 600 to 1000 C and the pressure ranges from 100 Torr to one atmosphere. Methane and hydrogen gases with methane content of 10% to 100% are used for the CNT synthesis. At high growth temperatures (greater than or equal to 900 C), the rapid inter-diffusion of the transition metal iron on the graphite surface results in the rough fiber surface without any CNT grown on it. When the growth temperature is relative low (650-800 C), CNT with catalytic particles on the nanotube top ends are fabricated on the graphite surface. (Methane and hydrogen gases with methane content of 10% to 100% are used for the CNT synthesis.) (By measuring the samples) Using micro Raman spectroscopy in the breath mode region, single-walled or multi-walled CNT (MWCNT), depending on growth concentrations, are found. Morphology, length and diameter of these MWCNT are determined by scanning electron microscopy and Raman spectroscopy. The detailed results of syntheses and characterizations will be discussed in the presentation.

Zhu, Shen↗
DOE OSTI2021

Nanowire-Based Materials as Coke-Resistant Catalyst Supports for Dry Methane Reforming

In this paper, nanowire-supported catalysts loaded with nickel are shown to be coke resistant compared to nanoparticle-supported catalysts. Specifically, Ni-loaded titania-based nanowire catalysts were tested with the dry methane reforming process in a laboratory-scale continuous packed-bed atmospheric reactor. The CO 2 conversion rate stayed above 90% for over 30 h on stream under coke-promoting conditions, such as high flow rates, low temperatures, and a high ratio of CH 4 to CO 2 . The coke (C x H y , x>>y) on the spent catalyst surface for both nanowire- and nanoparticle-supported catalysts was characterized by TGA, temperature-programmed reduction (TPR), and electron microscopy (SEM/TEM/EDS), and it was revealed that the types of carbon species present and their distribution over the morphology-enhanced materials played a major role in the deactivation. The CO 2 conversion activity of Ni supported on titania nanoparticles was reduced from ~80% to less than 72% in 30 h due to the formation of a graphitic coke formation. On the other hand, Ni particles supported on nanowires exhibited cube-octahedral morphologies, with a high density of non- (111) surface sites responsible for the increased activity and reduced graphitic coke deposition, giving a sustained and stable catalytic activity during a long time-on-stream experiment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2020

Impact Shock Origin of Diamonds in Ureilite Meteorites

The origin of diamonds in ureilite meteorites is a timely topic in planetary geology as recent studies have proposed their formation at static pressures >20 GPain a large planetary body, like diamonds formed deep within the Earth ́s mantle. We investigated fragments of three diamond-bearing ureilites (two from the Almahata Sitta polymict ureilite and one from the NWA 7983 main group ureilite). In NWA7983 we found an intimate association of large monocrystalline diamonds (up to atleast 100 μm), nanodiamonds, nanographite, and nanometric grains of metallic iron,cohenite, troilite and likely schreibersite. The diamonds show a striking texture pseudo morphing inferred original graphite laths.The silicates in NWA 7983 recorda high degree of shock metamorphism. The presence of both large mono crystalline diamonds and nano diamonds in a highly shocked ureilite can be explained by catalyzed transformation from graphite during an impact shock event characterized by peak pressures possibly as low as 15 GPa for relatively long duration (on the scale of few seconds). The formation of “large” (as opposed to nano-) diamond crystals could have been enhanced by the catalytic effect of metallic Fe-Ni-C liquid coexisting with graphite. We found no evidence that formation of micrometer(s)sized diamonds or associated Fe-S-P phases in ureilites require high static pressures and long formation times. It is unlikely that any of the diamonds in ureilites formed in bodies as large as Mars or Mercury.

Fabrizio Nestola↗
DOE OSTI2023

Catalyzed oxidation of nuclear graphite by simulated fission products Sr, Eu, and I

The influence of three fission products Sr, Eu, and I on the oxidation of IG-110 nuclear graphite was studied in the temperature range of 400 to 1000 °C. Sr and Eu were introduced as chlorides, and I was introduced as NaI. The temperature dependence of both CO 2 and CO production during the graphite oxidation measured with mass spectroscopy and infrared spectrometry shows that the introduction of these three compounds to graphite significantly decreases the onset temperature for the oxidation of graphite. Among the three compounds, NaI is the most active towards the oxidation reaction, characterized by a significant decrease of the onset temperature from approximately 650 to 400 °C before and after its introduction to graphite. Separate measurements of CO 2 and CO concentration at varying temperatures enable the calculation of the activation energy for the formation of CO 2 and CO. The activation energies for the oxidation of pure and fission product-impregnated graphite samples decrease in the following order: standard IG-110 graphite, EuCl 3 -impregnated IG-110, SrCl 2 -impregnated IG-110, and NaI-impregnated IG-110. This trend indicates that the three compounds catalyze the oxidation of graphite at temperatures relevant to the operation of high-temperature gas-cooled reactors. Furthermore, it is found that the three compounds can also affect the molar ratio of reaction products CO 2 and CO, and the rates of the graphite oxidation. At temperatures higher than about 850 °C, the impregnated samples exhibit lower CO 2 : CO ratios than the pure graphite. Different from EuCl 3 and NaI, the introduction of SrCl 2 decreases the graphite oxidation rates at temperatures higher than about 770 °C. Their catalytic mechanism can be understood based on a redox cycle of the intermediate active species, promoting the dissociation of molecular oxygen and transfer to the carbon.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2022

Valorizing the carbon byproduct of methane pyrolysis in batteries

While low-cost natural gas remains abundant, the energy content of this fuel can be utilized without greenhouse gas emissions through the production of molecular hydrogen and solid carbon via methane pyrolysis. In the absence of a carbon tax, methane pyrolysis is not economically competitive with current hydrogen production methods unless the carbon byproducts can be valorized. In this work, we assess the viability of the carbon byproduct produced from methane pyrolysis in molten salts as high-value-added anode or conductive additive for secondary Li-ion and Na-ion batteries. Raman characterization and electrochemical differential capacity analysis demonstrate that the use of molten salt mixtures with catalytically-active FeCl 3 - or MnCl 2 result in more graphitic carbon co-products. These graphitic carbons exhibit the best electrochemical performance (up to 272 mAh/g of reversible capacity) when used as Li-ion anodes. For all carbon samples studied here, disordered carbon domains and retained salt species trapped and/or intercalated into the carbon structure were identified by X-ray photoelectron and multinuclear solid-state nuclear magnetic resonance spectroscopy. The latter lead to reduced electrochemical activity and reversibility, and poorer rate performance compared to commercial carbon anodes. The electronic conductivity of the pyrolyzed carbons is found to be highly dependent on their purity, with the purest carbon exhibiting an electronic conductivity nearly on par with that of commercial carbon additives. These findings suggest that more effective removal of the salt catalyst could enable applications of these carbons in secondary batteries, providing a financial incentive for the large-scale implementation of methane pyrolysis for “low-carbon” hydrogen production.

08 HYDROGEN↗
DOE OSTI2021

Graphitized Biocarbon Derived from Hydrothermally Liquefied Low-Ash Corn Stover

Graphitized biocarbon can be utilized for energy storage applications such as supercapacitors. The scientific community have geared their attention to obtain such value-added product from abundantly available and low-cost biomass feedstock agricultural residues such as corn stover. Lignocellulosic components embedded within the cell wall of biomass substrates can provide a fine template for enhanced ion storage, transport, and rate capabilities, desirable for electrochemical storage. Presented is the utilization of homogenized low ash content corn stover milled and sieved to desired specifications, which underwent hydrothermal liquefaction in the presence of Ni-based catalytic salts at 275 o C. The hydrochar obtained by solid residue extracted from the reaction slurry was washed to acid neutral and subjected to catalytic activation using ZnCl 2 , followed by thermal annealing at 400 o C for morphological and pore size enhancement of the resulting biochar. Carbonization was performed on acid neutralized hydrochar at 850 °C to further enhance pore structures and increase graphitization for improved conductivity. Catalytic materials exhibited a specific capacitance of 316 F g -1 and held a 100% retention beyond 10,000 cycles. BET, Raman, XRD, cyclic voltammetry, chronopotentiometry, and EIS are discussed herein.

Biomass↗
DOE OSTI2022

Metal-free carbocatalyst for room temperature acceptorless dehydrogenation of N-heterocycles

Catalytic dehydrogenation enables reversible hydrogen storage in liquid organics as a critical technology to achieve carbon neutrality. However, oxidant or base-free catalytic dehydrogenation at mild temperatures remains a challenge. Here, we demonstrate a metal-free carbocatalyst, nitrogen-assembly carbons (NCs), for acceptorless dehydrogenation of N-heterocycles even at ambient temperature, showing greater activity than transition metal–based catalysts. Mechanistic studies indicate that the observed catalytic activity of NCs is because of the unique closely placed graphitic nitrogens (CGNs), formed by the assembly of precursors during the carbonization process. The CGN site catalyzes the activation of C–H bonds in N-heterocycles to form labile C–H bonds on catalyst surface. The subsequent facile recombination of this surface hydrogen to desorb H 2 allows the NCs to work without any H-acceptor. With reverse transfer hydrogenation of various N-heterocycles demonstrated in this work, these NC catalysts, without precious metals, exhibit great potential for completing the cycle of hydrogen storage.

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

High-Platinum-Content Catalysts on Atomically Dispersed and Nitrogen Coordinated Single Manganese Site Carbons for Heavy-Duty Fuel Cells

Fuel cells for heavy-duty vehicles (HDVs) have attracted considerable attention because of their unique scalability, better fuel economy, the less demand for hydrogen refilling infrastructure. However, the potential application requires more stringent fuel cell durability up to 25,000 h. Membrane electrode assemblies (MEAs) made from platinum group metal (PGM) catalyst with relatively high loading 0.3 mgPt cm –2 play a crucial role in ensuring high-power and long-term durability. Integrating fine PGM nanoparticles and robust carbon support with strengthened interactions is critical for improving MEA performance and durability. Herein, a unique atomically dispersed and nitrogen coordinated single Mn site-rich carbon (M–N–C) support was developed for high content (40 wt%) platinum catalysts for the oxygen reduction reaction (ORR) cathode with reduced thickness. Compared with two controls studied in this work (e.g., a porous graphitic carbon-supported Pt and a commercial TKK Pt/C catalysts), the Pt (40 wt%)/Mn–N–C catalyst exhibited much enhanced catalytic activity and stability for the ORR in both aqueous acidic electrolyte and polymer electrolyte-based MEA. Here, we carefully elucidated the—role of the Mn–N–C support in promoting Pt catalyst concerning its high surface area, partially graphitic structure, and nitrogen dopants, providing better Pt nanoparticle dispersion, and strengthened interactions between Pt and carbon. Consequently, the MEA from the Pt (40 wt%)/Mn–N–C catalyst generated a 1.61 A cm –2 at 0.7 V based on HDV conditions (0.2 mgPt cm –2 and 250 kPa air). More importantly, the MEA is highly durable and can retain 1.31 A cm –2 at 0.7 V after 30,000 voltage cycles (~19% loss), surpassing the commercial Pt/C catalyst (loss of ~56%). Therefore, the Mn–N–C carbon-supported Pt catalyst holds a great promise to meet the challenging DOE target (1.07 A cm –2 at 0.7 V after 150,000 cycles) for HDVs.

25 ENERGY STORAGE↗
DOE OSTI2021

Intermetallic PtCo Catalysts with Enhanced Performance and Stability [Slides]

Pt-based catalysts need systematic modifications to be adapted to different applications (LDV or HDV). L1 0 -CoPt particles have been demonstrated as highly active and durable cathode materials for fuel cells. Colloidal synthesis can generate catalysts with highly uniform particles size but the removal of surfactants is challenging. Acid leaching warrants a Pt shell with certain thickness, which mitigates the Co leaching. Controlling the size of L1 0 -CoPt particles is a robust method to alter their catalytic behaviours and tailor the function of catalysts. Modifying the carbon features (e.g. porosity and graphitization) is an effective method to regulate the performance and stability of catalysts to adapt the catalysts to different applications.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2021

Mechanistic insight into the active centers of single/dual-atom Ni/Fe-based oxygen electrocatalysts

Single-atom catalysts with maximum metal utilization efficiency show great potential for sustainable catalytic applications and fundamental mechanistic studies. We here provide a convenient molecular tailoring strategy based on graphitic carbon nitride as support for the rational design of single-site and dual-site single-atom catalysts. Catalysts with single Fe sites exhibit impressive oxygen reduction reaction activity with a half-wave potential of 0.89 V vs. RHE. We find that the single Ni sites are favorable to promote the key structural reconstruction into bridging Ni-O-Fe bonds in dual-site NiFe SAC. Meanwhile, the newly formed Ni-O-Fe bonds create spin channels for electron transfer, resulting in a significant improvement of the oxygen evolution reaction activity with an overpotential of 270 mV at 10 mA cm –2 . We further reveal that the water oxidation reaction follows a dual-site pathway through the deprotonation of *OH at both Ni and Fe sites, leading to the formation of bridging O 2 atop the Ni-O-Fe sites.

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

Optimizing dicyandiamide pretreatment conditions for enhanced structure and electronic properties of polymeric graphitic carbon nitride

Graphitic carbon nitride, a polymeric semiconductor, possesses a distinctive electronic band structure and exceptional chemical stability, making it a highly promising material for various catalytic applications such as electrocatalysis, photocatalysis, and photo-electrocatalysis. However, its practical applications remain limited due to its low active site density and poor electrical conductivity. In this study, to overcome such limitations, we have conducted a thorough investigation to explore the impact of dicyandiamide (DCDA) precursor pretreatment prior to thermal polymerization to graphitic carbon nitride. The DCDA precursor was subjected to various pretreatment methods including grinding using mortar and pestle, recrystallization through stirring or probe sonication after dissolving in deionized water, and freeze drying, prior to thermal polymerization at 550 °C for 2 hours. The structural and morphological properties of the catalysts prepared were compared and characterized by X-ray diffraction (XRD), attenuated total reflectance–Fourier transform infrared (ATR-IR) spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) analysis while the electronic band gap properties were determined based on density functional theory (DFT) calculations for a set of crystalline systems having C/N ratios similar to those identified experimentally. In comparison to direct thermal polymerization, pretreated samples rendered the same product yield, diverse morphologies with flat or wrinkle structures, and reduced electrochemical resistance, making them suitable for use in various catalytic processes.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Siloxane Deposition on the Ni-YSZ Solid Oxide Fuel Cell Anode Exposed to Bio-Syngas

Siloxane, a common contaminant present in biogas, is known for adverse effects on cogeneration prime movers. In this study, the siloxane deposition products and mechanism in the solid oxide fuel cell nickel-yttria stabilized zirconia (Ni-YSZ) anode are investigated analytically and experimentally. An SOFC with Ni-YSZ anode and pure Ni/YSZ pellets were exposed to a simulated biogas-reformate fuel with octamethylcyclotetrasiloxane (D4) contamination at 750 °C. The electrochemical characterization results show that the SOFCs performance degradation caused by D4 contamination is irreversible. Morphology and XRD results illustrate that silicon and carbon deposition can both be detected in the anode and pellets. Graphite, SiC and SiO2 are all possible products based on the results of XRD test. Here, according to the formation of graphite and SiC, the new mechanism suggests that carbon is also an essential factor in siloxane contamination of Ni-YSZ anodes besides silicon, which can be explained by the catalytic and electrochemical analysis.

25 ENERGY STORAGE↗
DOE OSTI2024

Influence of gadolinium doping on structural, optical, and electronic properties of polymeric graphitic carbon nitride

Polymeric graphitic carbon nitride (gCN) materials have received great attention in the fields of photo and electrocatalysis due to their distinct properties in metal-free systems with high physicochemical stability. Nevertheless, the activity of undoped gCN is limited due to its relatively low specific surface area, low conductivity, and poor dispersibility. Doping Gd atoms in a gCN matrix is an efficient strategy to fine-tune its catalytic activity and its electronic structure. Herein, the influence of various wt% of gadolinium (Gd) doped in melon-type carbon nitride was systematically investigated. Gadolinium-doped graphitic carbon nitride (GdgCN) was synthesized by adding gadolinium nitrate to dicyandiamide during polymerization. The X-ray diffraction (XRD) and transmission electron microscopy (TEM) results revealed that the crystallinity and the morphological properties are influenced by the % of Gd doping. Furthermore, X-ray photoelectron spectroscopy (XPS) studies revealed that the gadolinium ions bonded with nitrogen atoms. Complementary density functional theory (DFT) calculations illustrate possible bonding configurations of Gd ions both in bulk material and on ultrathin melon layers and provide evidence for the corresponding bandgap modifications induced by gadolinium doping.

36 MATERIALS SCIENCE↗
NASA NTRS2011

Synthesis of Stacked-Cup Carbon Nanotubes in a Metal Free Low Temperature System

Stacked-cup carbon nanotubes were formed by either Fischer-Tropsch type or Haber Bosch type reactions in a metal free system. Graphite particles were used as the catalyst. The samples were heated at 600 C in a gas mixture of CO 75 Torr, N2 75 Torr and H2 550 Torr for three days. Trans mission electron microscope analysis of the catalyst surface at the completion of the experiment recognized the growth of nanotubes. They were 10-50 nm in diameter and approximately 1 micrometer in length. They had a hollow channel of 5-20 nm in the center. The nanotubes may have grown on graphite surfaces by the CO disproportionation reaction and the surface tension of the carbon nucleus may have determined the diameter. Although, generally, the diameter of a carbon nanotube depends on the size of the cataly1ic particles, the diameter of the nanotubes on graphite particles was independent of the particle size and significantly confined within a narrow range compared with that produced using catalytic amorphous iron-silicate nanoparticles. Therefore, they must have an unknown formation process that is different than the generally accepted mechanism.

Kimura, Yuki↗
DOE OSTI2024

Mesophase pitch-based high performance carbon fiber production using coal extracts from mild direct coal liquefaction

Mild direct coal liquefaction (autogenous pressure, no catalyst, no H2 gas) of Springfield coal in fluid catalytic cracking decant oil is shown to effectively produce coal extract precursors to spinnable mesophase pitch. Here this work demonstrates that the coal extract can be thermally treated to obtain mesophase pitch in a facile one-step process, bypassing the production of an intermediate isotropic pitch. Furthermore, the presence of 25 wt.% coal in the initial slurry can increase the yield to mesophase pitch nearly twofold and yield to carbon fiber by approximately 70%. The coal extract-derived mesophase pitch was melt-spun and heat treated to produce carbon fiber with graphitic texture, high modulus (>400 GPa) and tensile strength up to 943 MPa. Overall, this work demonstrates that coal can be effectively utilized to markedly amplify the mesophase pitch and carbon fiber yield from fluid catalytic cracking decant oil by relatively simple processing, while conserving utility as a precursor to high performance carbon fiber and potentially other high value graphitic products.

36 MATERIALS SCIENCE↗
NASA NTRS1982

Coating for gasifiable carbon-graphite fibers

A thin, uniform, firmly adherent coating of metal gasification catalyst is applied to a carbon-graphite fiber by first coating the fiber with a film-forming polymer containing functional moieties capable of reaction with the catalytic metal ions. Multivalent metal cations such as calcium cross-link the polymer such as a polyacrylic acid to insolubilize the film by forming catalytic metal macro-salt links between adjacent polymer chains. The coated fibers are used as reinforcement for resin composites and will gasify upon combustion without evolving conductive airborne fragments.

Harper-Tervet, Jan↗