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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 OSTI2020

Quantifying thermal barrier coating delamination through luminescence modeling

Thermal barrier coatings (TBCs) are widely used in the hot sections of gas turbine systems as they are remarkably efficient in insulating the underlying superalloys, leading to higher operating temperatures and therefore enhancing the performance of the engines. However, this benefit is only possible if the integrity of the TBC under aggressive thermo-mechanical environments is ensured. Delamination is a common but hard to detect failure mode. We present, in this work, supported by experimentation, the implementation of a modeling approach applying the Kubelka-Munk theory to provide numerical quantification of luminescence contrast and intensity due to top coat delamination in TBCs. The method relies on the drastic change in reflectivity when a delamination forms, exploiting it for high-contrast luminescence mapping. Two distinct TBC configurations containing an erbium-doped yttria-stabilized zirconia (YSZ:Er 3+ ) layer for delamination sensing were used to validate this model. A delamination zone induced by Rockwell indentation was successfully tracked by measuring an increase of the intensity of the erbium emission line at 562 nm. Luminescence-based methods for delamination detection can provide a revolutionary non-invasive technique, with potential for both off-line and on-line engine monitoring.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Solid-State Sintering of Core-Shell Ceramic Powders Fabricated by Particle Atomic Layer Deposition

The properties of technical ceramics are highly dependent on their microstructure, which evolves during sintering. Sintering is the process by which ceramic parts are subjected to high temperatures to activate chemical diffusion and the consumption of porosity. During the initial stage of sintering, interparticle necks between neighboring particles form and subsequently increase in size, consuming porosity as the particle centers move closer together. To experimentally determine how this process depends on particle surface composition, particle atomic layer deposition (ALD) was used to deposit a thin film of amorphous aluminum oxide (Al2O3) onto yttria-stabilized tetragonal zirconia (3YSZ) particles, producing core-shell structured powders. The uniformity of the Al2O3 film was confirmed with transmission electron microscopy and energy dispersive spectroscopy. Scanning electron microscopy was used to observe microstructural evolution during sintering, and the dihedral angles of Al2O3 and 3YSZ grains were measured to determine the ratio of interfacial energies between the 3YSZ|3YSZ, 3YSZ|Al2O3, and Al2O3|Al2O3 interfaces. Analysis of the densification kinetics revealed that the initial stage of densification is dependent on the material at the surface of the particles (ie, the Al2O3 film) and is controlled by the diffusion of Al3+ cations through Al2O3. Once the Al2O3 film has coalesced, the sintering behavior is controlled by the densification of the core material (3YSZ). Thus, core-shell powders fabricated by particle ALD sinter by a two-step process where the kinetics are dependent on the material present at interparticle contacts.

alumina↗
DOE OSTI2021

Development of High Temperature (>700°C) molten Salt Pump Technology for Gen3 Solar Power Tower Systems

Generation 3 Concentrating Solar Power (CSP) Systems require thermal energy storage that can efficiently receive solar heat and deliver it to a working fluid at temperatures greater than 700°C. For liquid systems, the thermal transfer fluid must be phase stable over large temperature ranges. High temperature molten salts meet this criteria, but are difficult liquids to handle. The high heat and salt content can be very corrosive to several different materials that are wetted by the liquid salt. For power tower collectors, the molten salt must be pumped under high pressure to the top of the collector tower. These pumps have impellers and shafts as part of their rotating elements, and under load, require bearings to control shaft movement while rotating. These high temperature pumps require submerged bearings, and thus bearing materials that can withstand the temperature and molten salt contact over long periods of time. This is essential for keeping pump maintenance costs low, and downtime to a minimum. Long running bearing materials is an enabling technology for integrated liquid systems in Generation 3 CSP Systems. Keeping costs low and systems reliable are critical for the broad adoption of Gen 3 CSP Systems. Hayward Tyler, Inc (HTI) proposed development of journal bearing materials for use in vertical pumps designed for pumping high temperature molten salt on both the hot and cold sides of the solar power tower. To complete this objective, HTI utilized the testing capabilities of Oak Ridge National Laboratory (ORNL) and High Temperature System Design (HTSD). Materials would first be selected for static corrosion testing, then downselected for tribological testing. Successful tribologically tested materials would then be downselected for use in additional test regimes. Ten samples were selected for static corrosion testing. Three passed the static testing regime. Two of these materials were downselected for ball material in tribological testing against three metallic alloys: Sintered Y2O3 Partially Stabilized Zirconia YTZP and Silicon Nitride, Grade 147-31N. HTI also proposed collecting data from a thorough bearing test regime using a test rig designed and built as part of this project, and also a conceptual design for a high temperature molten salt vertical pump. HTI withdrew from the project prior to completion of this work and this report reflects only the work completed prior to withdrawal. The completed work produced two papers, one manuscript submitted for publication, and one paper published in the journal Solar Energy Materials and Solar Cells. The papers are: “Tribological behavior of ceramic-alloy bearing contacts in molten salt lubrication for concentrating solar power” and “Material Selection and Corrosion Studies Of Candidate Bearing Materials For Use In Molten Chloride Salt."

14 SOLAR ENERGY↗
DOE OSTI2022

Na Promotion of Pt/m-ZrO 2 Catalysts for the Steam Reforming of Formaldehyde

The decomposition selectivity of formaldehyde during steam reforming was explored using unpromoted and sodium promoted Pt/m-ZrO 2 catalysts, and the Na content was varied (0.5%Na, 1%Na, 1.8%Na, 2.5%Na, and 5%Na). In situ DRIFTS experiments during temperature programmed reaction in flowing H 2 O revealed that formaldehyde is adsorbed at reduced defect sites on zirconia, where it is converted to formate species through the addition of labile bridging OH species. Formate species achieve a maximum intensity in the range of 125–175 °C, where only slight changes in intensity are observed. Above this temperature, the formate decomposition reactivity strongly depends on the Na loading, with the optimum loadings being 1.8%Na and 2.5%Na. CO 2 temperature programmed desorption results, as well as a greater splitting observed between the formate ν asym (OCO) and ν sym (OCO) bands in infrared spectroscopy, indicate greater basicity is induced by the presence of Na. This strengthens the interaction between the formate -CO 2 functional group and the catalyst surface, weakening the formate C-H bond. A shift in the ν(CH) band of formate to lower wavenumbers was observed by addition of Na, especially at 1.8%Na and higher loadings. This results in enhanced decarboxylation and dehydrogenation of formate, as observed in in situ DRIFTS, temperature-programmed reaction/mass spectrometry experiments of the steam reforming of formaldehyde, and fixed bed reaction tests. For example, 2.5%Na addition of 2.5% increased the CO 2 selectivity from 83.5% to 99.5% and the catalysts achieved higher stable conversion at lower temperature than NiO catalysts reported in the open literature. At 5%Na loading, Pt sites were severely blocked, hindering H-transfer.

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

Promoting the Selectivity of Pt/m-ZrO 2 Ethanol Steam Reforming Catalysts with K and Rb Dopants

The ethanol steam reforming reaction (ESR) was investigated on unpromoted and potassium- and rubidium-promoted monoclinic zirconia-supported platinum (Pt/m-ZrO 2 ) catalysts. Evidence from in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) characterization indicates that ethanol dissociates to ethoxy species, which undergo oxidative dehydrogenation to acetate followed by acetate decomposition. The acetate decomposition pathway depends on catalyst composition. The decarboxylation pathway tends to produce higher overall hydrogen selectivity and is the most favored route at high alkali loading (2.55 wt.% K and higher or 4.25 wt.% Rb and higher). On the other hand, decarbonylation is a significant route for the undoped catalyst or when a low alkali loading (e.g., 0.85% K or 0.93% Rb) is used, thus lowering the overall H 2 selectivity of the process. Results of in situ DRIFTS and the temperature-programmed reaction of ESR show that alkali doping promotes forward acetate decomposition while exposed metallic sites tend to facilitate decarbonylation. In previous work, 1.8 wt.% Na was found to hinder decarbonylation completely. Due to the fact that 1.8 wt.% Na is atomically equivalent to 3.1 wt.% K and 6.7 wt.% Rb, the results show that less K (2.55% K) or Rb (4.25% Rb) is needed to suppress decarbonylation; that is, more basic cations are more efficient promoters for improving the overall hydrogen selectivity of the ESR process.

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

CO 2 Hydrogenation: Na Doping Promotes CO and Hydrocarbon Formation over Ru/m-ZrO 2 at Elevated Pressures in Gas Phase Media

Sodium-promoted monoclinic zirconia supported ruthenium catalysts were tested for CO 2 hydrogenation at 20 bar and a H 2 :CO 2 ratio of 3:1. Although increasing sodium promotion, from 2.5% to 5% by weight, slightly decreased CO 2 conversion (14% to 10%), it doubled the selectivity to both CO (~36% to ~71%) and chain growth products (~4% to ~8%) remarkably and reduced the methane selectivity by two-thirds (~60% to ~21%). For CO 2 hydrogenation during in situ DRIFTS under atmospheric pressure, it was revealed that Na increases the catalyst basicity and suppresses the reactivity of Ru sites. Higher basicity facilitates CO 2 adsorption, weakens the C–H bond of the formate intermediate promoting CO formation, and inhibits methanation occurring on ruthenium nanoparticle surfaces. The suppression of excessive hydrogenation increases the chain growth probability. Decelerated reduction during H 2 -TPR/TPR-MS and H 2 -TPR-EXAFS/XANES at the K-edge of ruthenium indicates that sodium is in contact with ruthenium. A comparison of the XANES spectra of unpromoted and Na-promoted catalysts after H 2 reduction showed no evidence of a promoting effect involving electron charge transfer.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Rare Earth and Transition Metal Containing Glasses

Transition metal (TM) and rare earth (RE) ions have been incorporated into many glass systems such as silicate, phosphate, and borosilicate-based oxide glasses, as well as in halide and chalcogenide glasses, that find applications ranging from optical, photonic, and magnetic devices, solid-state battery, to nuclear waste disposal. Understanding the structural role of RE and TM in these glasses can help to develop glass compositions for targeted applications with either high-optical emission efficiency, electrical conductivity, or chemical durability. In this chapter, we first provide a general introduction of the applications and structural features of RE and TM in glasses, then the critical aspects of molecular dynamics (MD) simulations of these glasses such as interatomic potentials, structural analysis tools to study RE and TM ions in glasses and their clustering behaviors, Quantitative Structure–Property Analysis (QSPR), diffusion and dynamic property calculations, and electronic structure calculations to understand electronic defects such as charge trapping and radiation effects are introduced. Three representative case studies are presented: the first one is on MD simulations of erbium- and europium-doped silica and silicate glasses, as well as cerium doped aluminophosphate glasses, that revealed the effect of glass composition on RE ion local structure and clustering behavior. Electronic structure calculations of cerium-doped glass show how the existence of multioxidation states help to mediate radiation-induced damages caused by excited electron–hole pairs was also discussed. The second one focuses on alkali vanadophosphate glasses where the existence of two vanadium oxidation states help to provide electronic conduction in the glasses while alkali ions provide ionic conduction. MD simulations were used to understand vanadium environments and other structural aspects in the phosphate glasses, as well as the ionic transport behaviors of alkali ions. The third case study is on zirconium-containing borosilicate and aluminosilicate glasses that find wide applications in nuclear waste disposal. MD simulations help to provide structural details of zirconium ions that are validated by diffraction and EXAFS spectra. The structural information was used to interpret changes of mechanical properties and chemical durability by using QSPR and other analyses-based MD-generated structure models.

Du, Jincheng↗
DOE OSTI2020

Filament-Free Bulk Resistive Memory Enables Deterministic Analogue Switching

Digital computing is nearing its physical limits as computing needs and energy consumption rapidly increase. Analogue-memory-based neuromorphic computing can be orders of magnitude more energy efficient at data-intensive tasks like deep neural networks, but has been limited by the inaccurate and unpredictable switching of analogue resistive memory. Filamentary resistive random access memory (RRAM) suffers from stochastic switching due to the random kinetic motion of discrete defects in the nanometer-sized filament. Here, this stochasticity is overcome by incorporating a solid electrolyte interlayer, in this case, yttria-stabilized zirconia (YSZ), toward eliminating filaments. Filament-free, bulk-RRAM cells instead store analogue states using the bulk point defect concentration, yielding predictable switching because the statistical ensemble behavior of oxygen vacancy defects is deterministic even when individual defects are stochastic. Both experiments and modeling show bulk-RRAM devices using TiO2-X switching layers and YSZ electrolytes yield deterministic and linear analogue switching for efficient inference and training. Bulk-RRAM solves many outstanding issues with memristor unpredictability that have inhibited commercialization, and can, therefore, enable unprecedented new applications for energy-efficient neuromorphic computing. Beyond RRAM, this work shows how harnessing bulk point defects in ionic materials can be used to engineer deterministic nanoelectronic materials and devices.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Epitaxial Ferroelectric Hf 0.5 Zr 0.5 O 2 with Metallic Pyrochlore Oxide Electrodes

The synthesis of fully epitaxial ferroelectric Hf 0.5 Zr 0.5 O 2 (HZO) thin films through the use of a conducting pyrochlore oxide electrode that acts as a structural and chemical template is reported. Such pyrochlores, exemplified by Pb 2 Ir 2 O 7 (PIO) and Bi 2 Ru 2 O 7 (BRO), exhibit metallic conductivity with room-temperature resistivity of <1 mΩ cm and are closely lattice matched to yttria-stabilized zirconia substrates as well as the HZO layers grown on top of them. Evidence for epitaxy and domain formation is established with X-ray diffraction and scanning transmission electron microscopy, which show that the c-axis of the HZO film is normal to the substrate surface. The emergence of the non-polar-monoclinic phase from the polar-orthorhombic phase is observed when the HZO film thickness is ≥≈30 nm. Furthermore, thermodynamic analyses reveal the role of epitaxial strain and surface energy in stabilizing the polar phase as well as its coexistence with the non-polar-monoclinic phase as a function of film thickness.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Hydrogen Storage in Partially Exfoliated Magnesium Diboride Multilayers

Metal boride nanostructures have shown significant promise for hydrogen storage applications. However, the synthesis of nanoscale metal boride particles is challenging because of their high surface energy, strong inter- and intraplanar bonding, and difficult-to-control surface termination. Here, it is demonstrated that mechanochemical exfoliation of magnesium diboride in zirconia produces 3-4 nm ultrathin MgB 2 nanosheets (multilayers) in high yield. High-pressure hydrogenation of these multilayers at 70 MPa and 330 °C followed by dehydrogenation at 390 °C reveals a hydrogen capacity of 5.1 wt%, which is ≈50 times larger than the capacity of bulk MgB 2 under the same conditions. This enhancement is attributed to the creation of defective sites by ball-milling and incomplete Mg surface coverage in MgB 2 multilayers, which disrupts the stable boron-boron ring structure. The density functional theory calculations indicate that the balance of Mg on the MgB 2 nanosheet surface changes as the material hydrogenates, as it is energetically favorable to trade a small number of Mg vacancies in Mg(BH 4 ) 2 for greater Mg coverage on the MgB 2 surface. To conclude, the exfoliation and creation of ultrathin layers is a promising new direction for 2D metal boride/borohydride research with the potential to achieve high-capacity reversible hydrogen storage at more moderate pressures and temperatures.

08 HYDROGEN↗
DOE OSTI2023

Thermal Performance of Perovskite-Based Photovoltaics for Operation in Low Earth Orbit

Perovskite-based photovoltaics are attractive for applications in space. The space environment is harsh with ionizing radiation, atomic oxygen, UV radiation, extreme temperatures, and thermal cycling. Herein, the thermal performance of perovskite active layer and perovskite photovoltaic devices in low earth orbit is analyzed. A 1 μm silicon oxide layer coupled with 500 nm zirconia thin film aid in cell thermal management is determined. The residual stresses between various layers in a device are modeled and it is proved that thermally induced mechanical failure of the perovskite (time > 460 years) is unlikely during operating lifetime of any mission. In conclusion, target power conversion efficiencies are also shared to manage maximum operating temperature of a perovskite-based device.

14 SOLAR ENERGY↗
DOE OSTI2020

Calcium Phosphate Catalysts for Ethanol Coupling to Butanol and Butadiene

The catalytic conversion of ethanol to butanol and butadiene at 633 K and atmospheric pressure (7 vol% ethanol) was studied over calcium phosphate materials pretreated over a wide temperature range. For calcium phosphate pretreated at or below 923 K, the resulting solid had an apatite structure identified by X-ray diffraction and strong acid sites probed by triethylamine (TEA) adsorption microcalorimetry. The low temperature pretreated materials were not effective at ethanol coupling reactions but instead were highly selective to acid-catalyzed products ethene and diethyl ether. Pretreatment of calcium phosphate at 973 K transformed the apatite structure to β-tricalcium phosphate, which exposed both acid and base sites evaluated by TEA and CO 2 adsorption microcalorimetry. In conclusion, high temperature pretreated calcium phosphate catalysts formed the coupling products butanol and butadiene during ethanol reaction. The butadiene selectivity was improved by supporting calcium phosphate on zirconia.

09 BIOMASS FUELS↗
DOE OSTI2022

The Effect of APS-HVOF Bond Coating Thickness Ratio on TBC Furnace Cycle Lifetime

In this work, combinations of NiCoCrAlY APS and high-velocity oxygen fuel (HVOF) bond coatings were deposited on alloy 247 disk substrates with APS yttria-stabilized zirconia (YSZ) top coatings to assess the benefit of air plasma sprayed (APS) ‘flash’ bond coatings. Using 1-h cycles at 1100 °C in air with 10% H 2 O and HVOF-only and APS-only bond coatings as a baseline, it was found that APS flash coatings extended the average coating lifetime by 16% to 35% with the thicker flash coating performing best. Principal component analysis and energy dispersive spectroscopy (EDS) compositional mapping on coatings characterized after 0, 100, 300 and 500 cycles and after failure showed that the Al in the bond coatings was depleted due to both oxidation and back diffusion into the substrate. The APS-only bond coating had significant oxidation throughout the bond coating and was so depleted in Al, that Al diffused from the substrate to the coating. Residual stress maps of the thermally-grown alumina scale were obtained every 100 cycles using photo-stimulated luminescence piezospectroscopy (PLPS) revealing that the Thick Flash coating had the slowest rate of damage accumulation in the oxide scale.

alumina scale↗
DOE OSTI2023

Activity of Brønsted Acid Sites in UiO-66 for Cyclohexanol Dehydration

Brønsted-acid sites are introduced via –OSO 3 H groups on the coordinatively unsaturated ZrO 2 nodes of UiO-66 metal organic frameworks (MOF). Such groups create strong Brønsted acidic sites that are active for cyclohexanol and ethanol dehydration (in liquid organic phase and gas phase, respectively). The intrinsic activity of Brønsted acid sites at nodes increased by increasing the concentration of sulfur, which is attributed to a shift from isolated µ 3 -OSO 3 H to two groups [(µ 3 -OSO 3 H) 2 ] interacting via hy-drogen bonding. For cyclohexanol dehydration, the relatively low activation enthalpies and negative transition entropies point to an E2 elimination mechanism, similar to dehydration with MFI zeolites in organic solvents. Furthermore, our results, show that the catalytic activity can be manipulated via the functionalization of zirconia nodes of the MOF framework.

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

Micro-cold Spray Deposition of YSZ Films from Ultrafine Powders Using a Pressure Relief Channel Nozzle

Abstract The use of ultrafine powders in the micro-cold spray (MCS) process, also referred to as the aerosol deposition method, typically results in porous and/or poorly adhering films because the particles do not impact at a high enough velocity for sufficient plastic deformation and interparticle bonding to occur. Under typical operating conditions, particles < 100 nm accelerate to high velocities but then are slowed by the stagnant gas in the bow shock that forms just upstream of the substrate. Using larger particles reduces particle slowing, but large particles can cause erosion of the film at high impact velocity, decreasing deposition efficiency. In this study, a pressure relief channel nozzle using helium as a carrier gas is proposed such that high-velocity deposition of yttria-stabilized zirconia particles as small as 10 nm in diameter is possible. This is well below the size range of powders previously used for MCS. The proposed nozzle design increases impact velocities for 10, 20, and 50 nm particles by ~ 880, 560, and 160 m/s, respectively, when compared to a conventional nozzle. Experimental deposition of ultrafine 8YSZ powder shows that the pressure relief channel nozzle results in lower porosity and more uniform deposits, with a ∼ 186% increase in deposition efficiency.

Materials Science↗
DOE OSTI2021

Exploring the Role of Humidity, Temperature, and Mixed Ionic and Electronic Conductivity on SOFC Anode Electrocatalysis

Infiltration of nanoscale electrocatalysts into Ni/yttria-stabilized zirconia (Ni-YSZ) cermets has been shown to improve the electrochemical performance of solid oxide fuel cell (SOFC) anodes. While infiltrated electrodes in SOFCs result in improved cell performance, long-term operation leads to coarsening of the infiltrated nanoparticles and negates the short-term performance improvements. This study explores the roles of humidity, temperature, and number of cycles of nanocatalyst infiltration in improving mixed conduction within the Ni-YSZ electrode. Two mixed conduction phases were studied: Gd 0.1 Ce 0.9 O 2-δ (GDC) as an infiltrant into Ni-YSZ electrodes, and Ni/transition metal doped-YSZ electrodes infiltrated with Ni. Analysis of impedance data from these cells shows improved electrochemical performance in infiltrated cells with mixed conduction compared with infiltrated cells containing purely ionic and electronic conducting phases. Improved anode performance is attributed to the availability of electronic pathways through predominantly ionic-conducting phases to connect distant Ni nanoparticles and/or Ni grains.

25 ENERGY STORAGE↗
DOE OSTI2022

Effects of bridging fibers on the evolution of lamellar architecture during H 2 /H 2 O redox cycling of Fe-foams

Fe/Fe 3 O 4 redox cycling via cyclic H 2 /H 2 O exposure at 800 °C is studied in lamellar Fe foams with 15 vol% fibers, created by freeze-casting. Fibers were integrated in the foams to mitigate densification during cycling by mechanically supporting neighboring lamellae, thus preventing buckling and sintering at contact points. Three fiber types are examined: short (0.1 mm) and long (1–2 mm) stainless-steel fibers, and long zirconia fibers. Long fibers bridge lamellae and have a marked effect on the architecture by increasing the initial interlamellar porosity (from < 60 to > 85%), with a corresponding decrease in foam shrinkage during initial reduction and sintering (from > 80 to < 55% volumetric loss). Though performance improves as compared to fiber-free foams, fiber effectiveness against damage decreases with cycling: after 10 redox cycles, porosity falls from 85 to 50% for foams with long fibers. One novel degradation mechanism is identified: fiber engulfment. This mechanism occurs over successive redox cycles, as material from the lamellae cyclically engulfs (as Fe 3 O 4 ) and withdraws (as Fe) from the fibers, with a net transport from lamellae to fibers after each cycle. Finally, this cyclic coarsening mechanism alters foam architecture from bridged-lamellar (with evenly distributed porosity) to mixed lamellar/fibrous (with unevenly distributed porosity).

36 MATERIALS SCIENCE↗
DOE OSTI2022

A general strategy and a consolidated mechanism for low-methane hydrogenolysis of polyethylene over ruthenium

Polyethylene (PE) is one of the most environment-threatening plastic waste. Its Ru-catalyzed hydrogenolysis is rapid but produces too much methane. Here, in this study, low-density PE hydrogenolysis is performed at mild conditions and short times over Ru-doped zirconia catalysts (Ru-XZr, X = Ti, Nb, Ce, W, V, Mo, Fe) to determine low-methane catalysts. Methane is produced via direct terminal C-C scission and surface cascade of consecutive C-C scissions, with the latter sensitive to hydrogen availability and dominant in hydrogen-lean conditions. Reactivity studies, characterization and theory reveal that the most effective dopant oxides (W, V, and Mo) are intermediately reducible, as they store and supply extra hydrogen to Ru via reverse hydrogen spillover. This hydrogen readily hydrogenates and desorbs long alkyl surface intermediates that would otherwise produce cascade methane. Our proposed mechanism reconciles the low methane production achieved by increasing the hydrogen pressure or reducing the particle size and exposes the key selectivity descriptors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗