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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 235 records · Page 13
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Low-temperature dechlorination of polyvinyl chloride (PVC) for production of H 2 and carbon materials using liquid metal catalysts

Polyvinyl chloride (PVC) is ubiquitous in everyday life; however, it is not recycled because it degrades uncontrollably into toxic products above 250°C. Therefore, it is of interest to controllably dechlorinate PVC at mild temperatures to generate narrowly distributed carbon materials. We present a catalytic route to dechlorinate PVC (~90% reduction of Cl content) at mild temperature (200°C) to produce gas H 2 (with negligible coproduction of corrosive gas HCl) and carbon materials using Ga as a liquid metal (LM) catalyst. A LM was used to promote intimate contact between PVC and the catalytic sites. During dechlorination of PVC, Cl is sequestrated in the carbonaceous solid product. Later, chlorine is easily removed with an acetone wash at room temperature. The Ga LM catalyst is reusable, outperforms a traditional supported metal catalyst, and successfully converts (untreated) discarded PVC pipe.

36 MATERIALS SCIENCE↗
NASA NTRS2005

Growing Aligned Carbon Nanotubes for Interconnections in ICs

A process for growing multiwalled carbon nanotubes anchored at specified locations and aligned along specified directions has been invented. Typically, one would grow a number of the nanotubes oriented perpendicularly to a silicon integrated-circuit (IC) substrate, starting from (and anchored on) patterned catalytic spots on the substrate. Such arrays of perpendicular carbon nanotubes could be used as electrical interconnections between levels of multilevel ICs. The process (see Figure 1) begins with the formation of a layer, a few hundred nanometers thick, of a compatible electrically insulating material (e.g., SiO(x) or Si(y)N(z) on the silicon substrate. A patterned film of a suitable electrical conductor (Al, Mo, Cr, Ti, Ta, Pt, Ir, or doped Si), having a thickness between 1 nm and 2 m, is deposited on the insulating layer to form the IC conductor pattern. Next, a catalytic material (usually, Ni, Fe, or Co) is deposited to a thickness between 1 and 30 nm on the spots from which it is desired to grow carbon nanotubes. The carbon nanotubes are grown by plasma-enhanced chemical vapor deposition (PECVD). Unlike the matted and tangled carbon nanotubes grown by thermal CVD, the carbon nanotubes grown by PECVD are perpendicular and freestanding because an electric field perpendicular to the substrate is used in PECVD. Next, the free space between the carbon nanotubes is filled with SiO2 by means of CVD from tetraethylorthosilicate (TEOS), thereby forming an array of carbon nanotubes embedded in SiO2. Chemical mechanical polishing (CMP) is then performed to remove excess SiO2 and form a flat-top surface in which the outer ends of the carbon nanotubes are exposed. Optionally, depending on the application, metal lines to connect selected ends of carbon nanotubes may be deposited on the top surface. The top part of Figure 2 is a scanning electron micrograph (SEM) of carbon nanotubes grown, as described above, on catalytic spots of about 100 nm diameter patterned by electron-beam lithography. These and other nanotubes were found to have lengths ranging from 2 to 10 m and diameters ranging from 30 to 200 nm, the exact values of length depending on growth times and conditions and the exact values of diameter depending on the diameters and thicknesses of the catalyst spots. The bottom part of Figure 2 is an SEM of an embedded array of carbon nanotubes after CMP.

Li, Jun↗
DOE OSTI2021

Quasi-Two-Dimensional Earth-Abundant Bimetallic Electrocatalysts for Oxygen Evolution Reactions

The extremely large surface area offered by quasi-two-dimensional (2D) nanostructures is a great advantage for catalytic applications. While bimetallic materials have been discovered as a group of promising catalysts for electrochemical water splitting, a facile and reliable synthesis approach toward 2D morphology to fully release its electrochemical catalytic potential is still lacking. In this work, bimetallic Co–Mo–O ultrathin nanosheets were synthesized by ionic layer epitaxy with controlled composition ratio. The Co–Mo–O nanosheets exhibited a quadrangle shape with a uniform thickness of ~2.5 nm. This 2D morphology largely enriched the surface catalytic active site ratio. Particularly, nanosheets with 2:1 Co-to-Mo ratio showed a substantially enhanced OER catalytic activity with a 3 orders of magnitude higher mass activity compared to benchmark IrO 2 and RuO 2 in an alkaline environment. Furthermore, this study introduces a promising possibility for creating high-performance electrocatalysts from 2D bimetallic materials with a high efficiency for material utilization.

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

Dual function materials (Ru+Na 2 O/Al 2 O 3 ) for direct air capture of CO 2 and in situ catalytic methanation: The impact of realistic ambient conditions

Here a dual function material (DFM) comprised of 1% Ru, 10% Na 2 O/γ–Al 2 O 3 was studied for combined direct air capture (DAC) of CO 2 and catalytic methanation in a temperature swing operation. In the newly proposed operation, the DFM captures CO 2 (400 ppm) from air at ambient conditions. The material is then heated in H 2 to a temperature sufficient for catalytic conversion of the captured CO 2 to renewable natural gas. In this study, we demonstrate high CO 2 adsorption capacity and rates at ambient conditions (25 °C); the adsorbed CO 2 is then successfully catalytically methanated upon heating in H 2 . Adsorption was also carried out in humid conditions, more closely simulating ambient air. Adsorption and methane production were greatly improved with stable initial performance. The rate of adsorption is shown to be flowrate-dependent, which is critical for future reactor design.

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

Plasma-Catalytic Ammonia Synthesis beyond the Equilibrium Limit

In this work, we explore the consequences of nonthermal plasma-activation on product yields in catalytic ammonia synthesis, a reaction that is equilibrium-limited at elevated temperatures. We employ a minimal microkinetic model that incorporates the influence of plasma-activation on N 2 dissociation rates to predict NH 3 yields into and across the equilibrium-limited regime. NH 3 yields are predicted to exceed bulk thermodynamic equilibrium limits on materials that are thermal-rate-limited by N 2 dissociation. In all cases, yields revert to bulk equilibrium at temperatures at which thermal reaction rates exceed plasma-activated ones. Beyond-equilibrium NH 3 yields are observed in a packed bed dielectric barrier discharge reactor and exhibit sensitivity to catalytic material choice in a way consistent with model predictions. The approach and results highlight the opportunity to exploit synergies between nonthermal plasmas and catalysts to affect transformations at conditions inaccessible through thermal routes.

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

A Review of Scalable Hexagonal Boron Nitride ( h -BN) Synthesis for Present and Future Applications

Hexagonal boron nitride (h-BN) is a layered inorganic synthetic crystal exhibiting high temperature stability and high thermal conductivity. As a ceramic material it has been widely used for thermal management, heat shielding, lubrication, and as a filler material for structural composites. Recent scientific advances in isolating atomically thin monolayers from layered van der Waals crystals to study their unique properties has propelled research interest in mono/few layered h-BN as a wide bandgap insulating support for nanoscale electronics, tunnel barriers, communications, neutron detectors, optics, sensing, novel separations, quantum emission from defects, among others. Realizing these futuristic applications hinges on scalable cost-effective high-quality h-BN synthesis. Here, in this work, the authors review scalable approaches of high-quality mono/multilayer h-BN synthesis, discuss the challenges and opportunities for each method, and contextualize their relevance to emerging applications. Maintaining a stoichiometric balance B:N = 1 as the atoms incorporate into the growing layered crystal and maintaining stacking order between layers during multi-layer synthesis emerge as some of the main challenges for h-BN synthesis and the development of processes to address these aspects can inform and guide the synthesis of other layered materials with more than one constituent element. Finally, the authors contextualize h-BN synthesis efforts along with quality requirements for emerging applications via a technological roadmap.

2D materials↗
DOE OSTI2020

Insights into the electronic origin of enhancing the catalytic activity of Co 3 O 4 for oxygen evolution by single atom ruthenium

The surface electronic structure of transition-metal oxide catalysts plays a decisive role in binding the intermediates of the oxygen evolution reaction (OER) to the oxide surface, in turn influencing the catalytic activity of these materials. However, the approaches to modulating the electronic structure of surface metal ions are rare and far behind the demands. Here, we report a surface single atom decoration for adjusting the surface electronic structure of Co 3 O 4 , leading to enhanced electrocatalytic activity for OER, in which the isolated Ru single atoms were uniformly deposited on the surface of Co 3 O 4 by an atomic layer deposition technology. As the OER catalyst, the as-made catalysts have exhibited a significantly enhanced catalytic activity (with increasing to 95.5 times) and a dramatically decreased overpotential. The density functional theory calculations reveal that the single-atom Ru acts as a promotor to adjust the 3d electronic structure of adjacent Co atoms and to tune the binding energy between intermediates and activity sites, finally leading to enhanced catalytic activity.

36 MATERIALS SCIENCE↗
NASA NTRS1989

Catalytic hollow spheres

The improved, heterogeneous catalysts are in the form of gas-impervious, hollow, thin-walled spheres (10) suitably formed of a shell (12) of metal such as aluminum having a cavity (14) containing a gas at a pressure greater than atmospheric pressure. The wall material may be, itself, catalytic or the catalyst can be coated onto the sphere as a layer (16), suitably platinum or iron, which may be further coated with a layer (18) of activator or promoter. The density of the spheres (30) can be uniformly controlled to a preselected value within .+-.10 percent of the density of the fluid reactant such that the spheres either remain suspended or slowly fall or rise through the liquid reactant.

Wang, Taylor G.↗
NASA NTRS1986

Catalytic hollow spheres

The improved, heterogeneous catalysts are in the form of gas-impervious, hollow, thin-walled spheres (10) suitably formed of a shell (12) of metal such as aluminum having a cavity (14) containing a gas at a pressure greater than atmospheric pressure. The wall material may be, itself, catalytic or the catalyst can be coated onto the sphere as a layer (16), suitably platinum or iron, which may be further coated with a layer (18) of activator or promoter. The density of the spheres (30) can be uniformly controlled to a preselected value within .+-.10 percent of the density of the fluid reactant such that the spheres either remain suspended or slowly fall or rise through the liquid reactant.

Wang, Taylor G.↗
DOE OSTI2026

Basal Plane Doping to Activate Colloidal MoS 2 Nanosheets for Catalytic Hydrodeoxygenation of para- Cresol

The valorization of biomass into biofuels is a critical process for producing renewable fuels. Hydrodeoxygenation (HDO), particularly over doped molybdenum disulfide (MoS 2 ), a transition metal dichalcogenide (TMD) material, is a common representative catalytic reaction system for converting biomass-derived materials into useful hydrocarbons. However, the location and role of dopants, such as Co, in HDO is not fully understood. The effects of dopant location and oxidation state are often precluded by inhomogeneity in the ensemble properties of nanosheet size and dopant dispersion, as well as difficulty in observing the behavior of atomic site behavior directly. Using a colloidal approach to synthesize cobalt-doped MoS 2 nanosheets with controlled dopant concentration, combined with X-ray absorption spectroscopy (XAS) and density functional theory (DFT) calculations, we determine that basal plane doped Co (25% Co:Mo mole ratio) shows peak catalytic activity in HDO of para-cresol, a model biomass-derived compound, and that basal Co sites are demonstrably more active than edge sites. By observing these doping effects in MoS 2 catalysts for HDO, we can further optimize not only the production of carbon-neutral fuels but also direct the tailoring of doped TMD catalysts toward their intended applications.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Nanofibrous electrocatalyst including nanofibrous continuous network of graphitic nanofibers having embedded catalytically active metal moieties

A nanofibrous catalyst and method of manufacture. A precursor solution of a transition metal based material is formed into a plurality of interconnected nanofibers by electro-spinning the precursor solution with the nanofibers converted to a catalytically active material by a heat treatment. Selected subsequent treatments can enhance catalytic activity.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Advanced Anode for Internal Reforming and Thermal Management in Solid Oxide Fuel Cells

Solid oxide fuel cell (SOFC) is an efficient and clean electrical power generation system compared to conventional combustion based technologies with energy efficiency reaching as high as 85-90% in co-generation mode (electricity and heat). Other advantages of SOFCs are hybridization, modularity of construction, small CO 2 foot print per kWh of generated electricity and fuel flexibility. Hydrocarbons present in the gaseous fuel is utilized in SOFCs by internal or external reforming. There are two different internal reforming concepts: Direct Internal Reforming (DIR) and Indirect Internal Reforming (IIR). For DIR operation, the endothermic reforming reaction and the exothermic reaction from the oxidation reaction are operated together in the single unit eliminating the requirement for a separate fuel reformer. This configuration also simplifies the overall system design, making SOFC more attractive and efficient means of producing electrical power. The main advantage of the DIR type of operation is that the H 2 or CO consumption by the electrochemical reaction could directly promote the conversion of methane at the anode side of the fuel cell resulting in high conversion and high efficiency. The DIR operation, however, requires an anode material that has desired dual catalytic (hetero and electro) properties for reforming reaction and electrochemical reactions. The anode materials also need to remain resistant to carbon formation at the operating temperature and atmosphere with stable cell performance. Another requirement is to match the reforming reactions and electrochemical reactions to avoid local cooling or overheating, which can result in mechanical failure due to thermally induced stresses. Direct internal reforming (DIR) of hydrocarbon fuels simplifies the overall SOFC system design making it more attractive and efficient for producing electrical power. Low cost alloy anodes for distributed internal reforming of methane and other hydrocarbon fuels offer increased fuel-flexibility, reliability, and long term performance stability of solid oxide fuel cells (SOFC). The research program examined modification of the chemical compositions and microstructure of high entropy alloy (HEA) anode materials using thermochemical calculations and process simulation and modeling to achieve distributed reforming over the entire anode to eliminate hot zones. Cell fabrication and testing of the HEA anodes using button cell configuration has been performed to demonstrate the advantages of new anode over traditional Ni-YSZ anodes for distributed reforming and carbon free operation. Technical accomplishments include identification and synthesis of HEA carbon-resistant anode, demonstration of reduction in reforming rate confirmed by GC and modelling data validating effectiveness for thermal management in cell/stacks, electrochemical testing of HEA anode in single cell (HEA-GDC||YSZ||LSM-YSZ) and Characterization of pretest and posttest anode materials by TEM and SEM-EDS confirming carbon-free operation.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2024

Building Artificial Layered Solids from the Bottom-up: Materials by Design to Enable New Energy Technologies

This final technical report summarizes the key accomplishments on this DOE Early Career Program award received by PI Guihua Yu at the University of Texas at Austin. The main goal of this ECP award was to develop synthetic methodologies, self-assembly approaches towards structurally controlled nanosheets-like solids from the bottom up, and to understand and characterize their chemical/physical characteristics for the design of future-generation energy devices with novel functions and properties, that will have direct implications for energy science and technologies such as energy storage and conversion, and catalysis. The project accomplished these goals by completing the following objectives: • Rational design, synthesis, and self-assembly of structurally-controlled molecular ‘nanosheets’ materials. Moving beyond conventional van der Waals two-dimensional crystals, this project enables new synthesis and processing strategies to develop ultrathin nanosheets materials, from inorganic transition-metal oxides-based, to hybrid organic-inorganic nanomaterials, with structural factors such as facet, thickness and pore structure being well controlled during synthesis or assembly processes. • Fundamental understanding and electrochemical characterization of these assembled molecular ‘nanosheets’ materials via charge/mass transport studies through electrochemical intercalation of different metal ions for next-generation energy storage, as well as electrocatalytic studies using this new material platform for understanding catalytic reaction kinetics and the roles of surface functionalization and interface interactions owing to atomic thickness, nanoscale porosity, and other structural factors.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Limits of Detection for EXAFS Characterization of Heterogeneous Single-Atom Catalysts

Single-atom catalysts (SACs), consisting of individual metal atoms dispersed on a support, attract attention due to their unique reactivity, efficient use of precious metals, and precise chemical tunability. Characterization of the metal species is crucial to substantiate structure–function relationships. Authors often use—and referees often require—X-ray absorption spectroscopy (XAS) data to prove the absence of clustered metal (or metal oxide) structures after pre-treatment and under in situ or operando conditions. However, there has been no critical assessment of the limitations of XAS in substantiating such conclusive statements, which is particularly important given the potential outsized influence of minority catalyst structures in dictating catalytic activity. Here, in this article, we quantitatively assess the detection limits of XAS to identify metal (or metal oxide) clusters in samples containing predominantly single atoms by modeling the extended X-ray absorption fine structure (EXAFS) of mixtures of structures. We identified that a significant fraction of clusters can coexist with SAC active sites (e.g., ~10% metallic Pt or ~40% oxidized Pt clusters in Pt/CeO 2 SACs), while eluding detection via EXAFS with any statistical significance. To generalize these conclusions, a descriptor-based screening of bulk metal oxides using a continuous Cauchy wavelet transform was proposed that suggests certain materials for which differentiating atomically dispersed metal species and metal oxide clusters would be infeasible by EXAFS (e.g., ReO x ). Based on this analysis, we suggest best practices for the study of SACs using EXAFS and provide recommendations to ensure that conclusions do not outpace the evidence used to support them. In this rapidly expanding research area, rigorous characterization will lead to greater understanding of the behavior of SACs and ultimately improved catalytic materials.

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

Measurement and Modeling of the effects of exhaust composition and hydrothermal aging on the ammonia storage capacity of a commercial Cu-SSZ-13 catalyst

Copper exchanged chabazites are among the state-of-the-art catalyst materials being studied for selective catalytic reduction of NOx, however, there is still a need to understand how these materials store ammonia after aging. In this work, studies are performed to assess the ammonia storage capacity of Cu-SSZ-13 as a function of concentration, temperature, and extent of hydrothermal aging. Ammonia binds at three difference sites: (i) a Cu site bound at 1 framework Al (Z 1 Cu site), (ii) a Cu site bound at 2 framework Al (Z 2 Cu site), and (iii) a Brønsted acid site (ZH site). Results show that a 3-site model can accurately capture ammonia storage across all conditions. Impacts for hydrothermal aging are considered via 3 aging reactions that change the site densities of each identified adsorption site. Model assessment shows that during aging there is a significant loss in Brønsted acid sites.

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

Advancements in cerium/titanium metal-organic frameworks: Unparalleled stability in CO oxidation

Due to the excellent catalytic properties of Ce-based materials, the development of thermally stable metal-organic frameworks (MOFs) based on Ce-oxo clusters has attracted significant attention but remains challenging. In this work, we report the synthesis of an unreported Ce 4 Ti 2 -TMA (Ce IV 4 Ti IV 2 O 4 (OH) 4 (C(CH 3 ) 3 COO) 12 ·3H 2 O·3MeCN) cluster, which serves as an ideal source for the assembly of robust Ce/Ti-MOFs. Using this cluster, we constructed two isostructural MOFs, denoted as NU-3000 and NU-3001. Single-crystal X-ray diffraction analysis confirms these MOFs as mesoporous structures with 12-coordinated Ce 3 Ti 3 nodes. Furthermore, structural analysis reveals a plane triangular node structure that likely contributes to the excellent thermal stability of these MOFs. Finally, both MOFs show catalytic activity toward high-temperature (250°C) CO oxidation and maintain significant porosity, emphasizing the thermal stability of these materials under practical catalytic conditions. Furthermore, the straightforward synthesis of thermally robust Ce/Ti-MOFs from the Ce 4 Ti 2 -TMA cluster will pave the way for future Ce/Ti-MOF-based catalyst development.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Kinetic and X-ray Absorption Spectroscopic Analysis of Catalytic Redox Cycles over Highly Uniform Polymetal Oxo Clusters

Metal–organic framework materials (MOFs) offer an opportunity for investigating catalytic properties of polymetal oxo clusters that are highly well defined and uniform in nature, in contrast to other classes of catalysts that may exhibit a propensity toward active site heterogeneity. We report herein a kinetic and X-ray absorption spectroscopy (XAS) analysis of the two-electron oxidation of CO over divalent metal sites in MIL-100(M = Fe, Cr) (MIL = Materials of Institut Lavoisier) materials carrying μ 3 -oxo bridged trimers, and connect observations about the kinetic relevance of redox steps to density functional theory (DFT) predictions published previously. The high degree of uniformity evident from in situ titration measurements leads to a congruence in mechanistic inferences made from steady-state catalytic, transient stoichiometric, isotopic exchange, and isotopic tracer data that all point to a sequential mechanism comprised of separate oxidation and reduction half-cycle steps conjoined by an active oxygen intermediate. In situ XAS data reinforce mechanistic conclusions derived from kinetic analysis, and suggest that the active oxygen intermediate may be more appropriately characterized as an iron-oxyl (Fe 3+ –O – ) rather than an iron-oxo (Fe 4+ =O 2– ) species. The Cr analogue of MIL-100 exhibits contrasting rate features that can be rationalized using an identical sequence of steps as MIL-100(Fe), but with a highly dissimilar set of kinetic parameters that can also be validated using transient stoichiometric experiments. The larger coverages of active oxygen intermediates on MIL-100(Cr) are consistent with predictions from prior DFT studies that suggest more stable and less reactive active oxygen species for metals with lower d-electron counts, and point to metal identity as a lever for precisely controlling the kinetic relevance of oxidation and reduction half-cycles in catalytic redox sequences over polymetal oxo clusters. Importantly, the results presented point to the utility of developing broadly applicable structure–catalytic property relationships over MOF nodes specifically, and highly uniform catalysts more generally.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗