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At least 991 records · Page 55
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Systems and methods for preparing butenes

Systems for preparing butenes are provided. The systems can include a reactor inlet coupled to both a reactor and at least one reactant reservoir; at least one of the reactant reservoirs containing one or both of an aldehyde and/or ethanol; a catalyst within the reactor, the catalyst comprising a metal component and an acidic support material; and a reactor outlet operationally configured to convey a butene-rich reaction product to a product reservoir. Methods for preparing butenes are also provided. The methods can include exposing one or both of ethanol and/or an aldehyde to a catalyst comprising a metal component and an acidic support to form a butene-rich product that comprises one or both of 1-butene and/or 2-butene.

Dagle, Vanessa↗
DOE OSTI2025

Effect of tert -Butyl Substitution on the Interactions of Cobalt Phthalocyanine with a Carbon Monoxide-Functionalized Tip

Supported cobalt phthalocyanines (CoPc) are promising catalysts for CO 2 reduction, a critical process for mitigating greenhouse gas emissions. Enhancing the catalytic performance of CoPc involves modifying the interaction between the cobalt center and intermediate species. This study focuses on the effects of tert-butyl substitution on CoPc using (tert-butyl) 4 CoPc, where the substitution can both directly alter the molecule’s intramolecular electronic structure and indirectly alter it by the bulky group weakening the interaction with the support. Toward this end, we investigated the structural and chemical properties of (tert-butyl) 4 CoPc on a Ag(111) surface at the single-molecule level using three-dimensional atomic force microscopy (AFM) with a CO-terminated tip and discussed them in comparison with data for unmodified CoPc and amino-substituted CoPc. Notably, distance-dependent force measurements revealed anomalies in the tert-butyl groups’ force curves, attributed to their rotational flexibility. The tert-butyl (t-butyl) groups were also observed to increase the attraction of the central Co atom to CO, but this effect was attributed largely to enhanced interactions of the back of the tip with the peripheral t-butyl groups. In conclusion, while this longer-range interaction would not be expected to impact the interaction of small molecules with the catalytic center, the results reveal the ability of AFM to characterize longer range environmental interactions that can enhance adsorption and subsequent reactions of larger molecules, as well as the role side chains that offer configurational adaptability may play in these interactions.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2023

Enhanced low temperature performance of bimetallic Pd/Pt/SiO 2 (core)@Zr(shell) diesel oxidation catalysts

Here, in this study, the diesel oxidation performance of degreened (DG) and hydrothermally aged monometallic and bimetallic Pd/Pt/SiO 2 (core)@Zr(shell) catalysts with varying Pd/Pt molar ratios from 3/1–1/3 was evaluated. Pd/Pt(3/1)/SiO 2 @Zr (DG) achieved 50% and 90% conversion of CO at 166 °C (T 50 ), 169 °C (T 90 ) and total hydrocarbons (THCs) at 198 °C (T 50 ), 244 °C (T 90 ). Decreasing the Pd/Pt molar ratio led to a decrease in the T 50,90 ’s, with Pd/Pt(1/3)/SiO 2 @Zr (DG) achieving T 50,90 ’s at 153, 156 °C for CO and 171, 200 °C for THCs, respectively. Moreover, Pd/Pt(1/3)/SiO 2 @Zr showed enhanced hydrothermal stability. XRD and TEM showed that in the hydrothermally aged bimetallic catalysts, the fraction of Pd present as a Pt-Pd metallic alloy increased with Pt content. The enhanced low temperature performance of Pd/Pt(1/3)/SiO 2 @Zr compared to the other studied catalysts was attributed to Pd being primarily present in metallic form, despite being subjected to severe oxidizing conditions.

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

Ethane dehydrogenation over manganese oxides supported on ZSM-5 zeolites

Mn-ZSM5 catalysts are shown to have high reaction rates, C 2 H 4 selectivity and stability for the ethane dehydrogenation reaction. The specific reaction rate increases with the Mn loading until the optimal Mn amount of 3.4 wt% for zeolites with a Si/Al ratio of 12. Structure characterizations and spectra analysis have unveiled that this catalyst contains MnO 2 nanoparticles on the zeolite external surface and (MnOH) + groups on the external surface of the zeolite. The MnO 2 nanoparticles contain the catalytic sites for ethane dehydrogenation while the (MnOH) + groups help stabilize the oxide particles, leading to the high stability of the Mn-ZSM5 catalyst for EDH. As a result, the Mn-ZSM5 samples can catalyze EDH for over 150 h at 600 °C with a high reaction rate (>10 mmol C 2 H 6 g cat –1 h –1 ) and high C 2 H 4 selectivity (>98%). Finally, the spent catalyst can also be regenerated by calcination in dry or wet air (3% steam).

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

Rational design of stable sulfur vacancies in molybdenum disulfide for hydrogen evolution

Sulfur (S) vacancies in MoS 2 have been found to act as a new active center, which shows an unprecedented intrinsic HER activity under elastic strain. However, such S-vacancies are unstable and the activities are very sensitive to the vacancy concentration. A strategy to stabilize these abundant active sites is thus highly desirable. Herein, we rationally design a catalyst system to stabilize S-vacancies in the basal plane of $2H-$MoS 2 supported on defective vertical graphene network (VGN). The energetically favorable line-shaped S-vacancies in MoS 2 shows a consistently high HER activity that is insensitive to S-vacancy concentration. Moreover, the defective graphene support effectively stabilizes these S-vacancies. The optimized catalyst exhibits a superior HER activity with overpotential of 128 mV at 10 mA cm -2 and Tafel slope of 50 mV dec -1 . Most importantly, the catalyst shows greatly increased stability over 500 h; benchmarking the most stable nonprecious HER catalyst in acidic media to date.

2D heterostructure↗
DOE OSTI2022

Ru Single Atoms on One-Dimensional CF@g-C 3 N 4 Hierarchy as Highly Stable Catalysts for Aqueous Levulinic Acid Hydrogenation

Herein, we report a stable catalyst with Ru single atoms anchored on a one-dimensional carbon fiber@graphitic carbon nitride hierarchy, by assembling wet wipes composed of fiber-derived carbon fiber (CF), melamine-derived graphitic carbon nitride (g-C3N4) and RuCl3 before NaBH4 reduction. The atomically dispersed Ru species (3.0 wt%) are tightly attached via N-coordination provided by exterior g-C3N4 nanosheets, and further stabilized by the interior mesoporous CF. The obtained CF@g-C3N4–Ru SAs catalyst can be cycled six times without notable leaching of Ru or loss of GVL yield in the acidic media. This catalyst is more stable than Ru nanoparticles supported on CF@g-C3N4, as well as Ru single atoms anchored on CF and g-C3N4, and proves to be one of the most efficient metal catalysts for aqueous LA hydrogenation to γ-valerolactone (GVL). The isolated Ru atoms by strong N-coordination, and their enhanced electron/mass transfer afforded by the one-dimensional hierarchy, can be responsible for the excellent durability of CF@g-C3N4–Ru SAs under harsh reaction conditions.

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

Development of a Sulfur Tolerant CHG Process (CRADA 442) (Final Report)

The Pacific Northwest Laboratory (PNNL) has developed the Catalytic Hydrothermal Gasification (CHG) technology, which can convert low-value organics dispersed in aqueous streams, such as the aqueous phase byproduct from hydrothermal liquefaction (HTL) of wet wastes, to a mixture of methane, H 2 , and CO 2 . The current CHG catalyst, ruthenium (Ru) on a graphite substrate, was selected for its effectiveness as a reducing catalyst. However, the target waste aqueous feedstock, the HTL aqueous phase from wet wastes, such as sewage sludge, contains a fair amount of sulfur in both organic and inorganic forms. Like many other reduced metal catalysts, Ru is deactivated or poisoned by exposure to sulfur, among other contaminants. In general, a deactivated Ru catalyst cannot be reactivated or restored except by removing and returning it for remanufacturing. Therefore, there is an urgent need for a sulfur-resistant catalyst to enable CHG processing of the HTL aqueous waste stream. PNNL, with support from SoCalGas CRADA, has developed a sulfur resistant CHG catalyst and demonstrated a stable CHG process for converting HTL aqueous phases from wet wastes. Here, we report the major accomplishments of the project: • We have demonstrated that sulfided Ru based catalysts is stable during CHG of HTL aqueous waste stream, with a requirement of activity improvement. • We have developed a new catalyst, with 0.5-2 wt.% Ru loading, showing better activity compared to the baseline 6.7 wt.% RuSx/C catalyst. • With the new catalysts, the single-pass COD reduction is approximately 60% and two-pass COD reduction can reach approximately 85%. • The process is robust in terms of being effective across a wide range of organic species in the feedstock. • Techno-economic analysis was conducted to evaluate the economic impact of catalyst advancement and identify further improvement requirements. This type of catalyst shows great potential to be efficient and robust for CHG with low catalyst cost.

03 NATURAL GAS↗
DOE OSTI2025

Exploring Atomic-Scale Interactions at the Interface of Reducible Oxide and Ruthenium Nanocatalyst for Ammonia Decomposition

Restructuring atomic-scale interfaces between noble metal nanoparticles and metal oxides provides a promising approach to enhancing catalytic properties. In this study, Ru nanoparticles were supported on CeO 2 , ZrO 2 , and HfO 2 via pyrolysis of MOFs under oxygen-suppressed high-temperature conditions. Despite its nearly ideal particle size (∼2.3 nm), the Ru–CeO 2 /C catalyst exhibited the lowest ammonia decomposition activity. X-ray absorption spectroscopy and DFT calculations revealed that electron transfer from Ru to CeO 2 formed positively charged Ru and partially reduced Ce 4+ , weakening the catalytic performance. In contrast, oxygen-deficient ZrO 2 and HfO 2 support donated electrons to Ru, preserving its metallic state. These findings demonstrate that the reducibility of oxide supports governs the direction and magnitude of interfacial charge transfer, directly tuning catalytic behavior. This study provides insights into the design of oxide-supported Ru catalysts for ammonia decomposition.

Catalysts↗
DOE OSTI2023

Size-Dependent Energy and Adhesion of Pd Nanoparticles on Graphene on Ni(111) by Pd Vapor Adsorption Calorimetry

Carbon-supported late transition-metal nanoparticles are promising catalysts and electrocatalysts for wide-ranging applications. However, experimental investigations of the bonding energetics of metal nanoparticles on carbon supports are very limited. Here, in this work, we report heats of adsorption of Pd vapor deposited onto single-layer graphene(0001) supported on Ni(111) at 100 and 300 K as Pd grows particles of well-defined size in the range from three atom clusters to 6 nm diameter. Sizes were determined from He + low-energy ion scattering (LEIS). In this size range, the differential heat of Pd adsorption increases from 228 kJ/mol to within 10 kJ/mol of the heat of sublimation of bulk Pd (377 kJ/mol). The chemical potential of metal atoms in these nanoparticles as a function of average particle size was determined from these results. The adhesion energy at the Pd/graphene(0001)/Ni(111) interface was extracted from these data and found to be 3.5 J/m 2 for the largest Pd particles. For the three metal elements that have now been studied (Pd, Ni, and Ag), we found an increase in metal/graphene(0001)/Ni(111) adhesion energy with metal carbophilicity, which we defined here as the heat of C atom adsorption on that metal’s (111) surface estimated from published density functional theory calculations.

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

Microwave-assisted ammonia synthesis over Ru/MgO catalysts at ambient pressure

Here, in this work, a fixed frequency (2.45 GHz) microwave (MW) was used to synthesis ammonia over Ru/MgO catalysts under ambient atmospheric pressure at 320 °C. The loading of Ru catalyst over MgO was varied at 4% and 10 wt %. The metal support interaction was found to play an important role not only catalytically but also altering the microwave-catalyst interaction affecting the ammonia formation rate. The higher metal loading (10 wt%) produced the most activity, stability, and energy efficiency. It was found the Ru was better dispersed at higher loading which decreased the sintering of the catalyst due to lower microwave energy needed to maintain the reaction temperature. Additional effects from the microwave can include enhanced electron movement and/or electric fields formed between the metal sites of the catalyst. The microwave reactor offers a quick on/off catalyst recovery, within 11 min, compared to thermal convectional Haber Bosch (HB) technology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1989

Oxygen electrodes for rechargeable alkaline fuel cells

Electrocatalysts and supports for the positive electrode of moderate temperature single-unit rechargeable alkaline fuel cells are being investigated and developed. Candidate support materials were drawn from transition metal carbides, borides, nitrides and oxides which have high conductivity (greater than 1 ohm/cm). Candidate catalyst materials were selected largely from metal oxides of the form ABO sub x (where A = Pb, Cd, Mn, Ti, Zr, La, Sr, Na, and B = Pt, Pd, Ir, Ru, Ni (Co) which were investigated and/or developed for one function only, O2 reduction or O2 evolution. The electrical conductivity requirement for catalysts may be lower, especially if integrated with a higher conductivity support. All candidate materials of acceptable conductivity are subjected to corrosion testing. Materials that survive chemical testing are examined for electrochemical corrosion activity. For more stringent corrosion testing, and for further evaluation of electrocatalysts (which generally show significant O2 evolution at at 1.4 V), samples are held at 1.6 V or 0.6 V for about 100 hours. The surviving materials are then physically and chemically analyzed for signs of degradation. To evaluate the bifunctional oxygen activity of candidate catalysts, Teflon-bonded electrodes are fabricated and tested in a floating electrode configuration. Many of the experimental materials being studied have required development of a customized electrode fabrication procedure. In advanced development, the goal is to reduce the polarization to about 300 to 350 mV. Approximately six support materials and five catalyst materials were identified to date for further development. The test results will be described.

Swette, L.↗
DOE OSTI2021

Highly Selective Carbon-Supported Boron for Oxidative Dehydrogenation of Propane

Bulk boron materials, such as hexagonal boron nitride (h-BN), are highly selective catalysts for the oxidative dehydrogenation of propane (ODHP). Previous attempts to improve the productivity of these systems involved the immobilization of boron on silica and resulted in less selective catalysts. Here, we report that acid-treated, activated carbon-supported boron prepared via incipient wetness impregnation with boric acid (B/OAC) exhibits equal propylene selectivity and improved productivity (kg propylene kg cat -1 hr -1 ) as compared to h-BN. Characterization of the fresh and spent catalysts with infrared, Raman, X-ray photoelectron, and solid-state NMR spectroscopies reveals the presence of oxidized/hydrolyzed boron that is clustered on the surface of the support.

03 NATURAL GAS↗
DOE OSTI2021

Solvothermal synthesis of MOF-derived supported Ru nanocatalysts for low-temperature ammonia synthesis

We report the synthesis and scale-up of Ru catalysts that use high porosity MOF templates grown on graphitic carbon supports via solvothermal synthesis. Thermal treatment of the MOF resulted in well-dispersed Ru nanoparticles that are fully stabilized by in-situ graphitization of the surrounding carbon. The resulting catalyst has demonstrated significant improvement in activity for low-temperature NH 3 synthesis, and catalyst production has been scaled up from 1 g per batch to 200 g per batch scales.

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

Adjusting the Criteria for Hydrogen Evolution by Single-Atom Catalysts

Downsizing noble metal catalysts is essential for improving atomic efficiency in sustainable energy applications. Typically, strategies focus on anchoring atomically scaled catalysts onto heteroatom-rich substrates, but these interactions can unintentionally alter the electronic structure of the catalyst, complicating the hydrogen evolution reaction (HER) mechanism. This study focuses on elucidating the interfacial mechanism of HER using structurally well-defined platinum single-atom (Pt SA) electrocatalysts. Unlike chemically reduced SAs, electrochemically deposited Pt SA catalysts do not rely on strong support interactions. As a result, these isolated Pt atoms can potentially achieve the theoretical maximum hydrogen production efficiency. This work introduces electrocatalysts composed solely of true SA sites, clarifying previous ambiguities surrounding the concept of SA electrocatalysis.

adsorption↗
DOE OSTI2026

Engineering CoO x ‑Based Self-Supported Anodes for Pure-Water-Fed Anion-Exchange-Membrane Electrolysis

Commercial membrane electrolyzers rely on acidic fluorocarbon membranes and ionomers, requiring the use of expensive IrO x -based oxygen-evolution catalysts. Anion-exchange-membrane water electrolyzers (AEMWEs) operate in an alkaline environment, enabling the use of non-precious-metal catalysts. Here, we study and engineer CoO x -based catalyst-coated anodes deposited via hydrothermal synthesis directly onto porous transport layers both with and without thermal annealing. The self-supported, nanoneedle-structured Co3O4 anode, formed by annealing the as-synthesized cobalt carbonate hydroxide, Co­(CO3) x (OH) y , outperforms the baseline Co3O4 nanoparticle ink-based anode in pure-water-fed AEMWE due to the improved catalyst-layer continuity and thus number of electroactive Co species. The as-synthesized and unannealed Co­(CO3) x (OH) y , however, appears to undergo substantial conversion to a more-active CoO x (OH) y phase predominantly at the surface, with nominal Co3+ present and higher electrical conductivity, lowering the cell voltage to ∼200 mV at 1.0 A·cm–2 in pure-water-fed AEMWE compared to the conventional Co3O4 nanoparticle anodes. We analyze the differences in electrode electrochemical response between pure-water and KOH feed modes, finding distinct activation and degradation modes. The Co­(CO3) x (OH) y anode shows significant activation and slower degradation linked to the conversion to oxyhydroxide. We propose catalyst layer designs that promote both hydroxide and electron transport, alongside interfacial engineering strategies to obtain high performance while mitigating anode degradation.

anion-exchange-membrane water electrolysis↗
DOE OSTI2025

Durable, pure water–fed, anion-exchange membrane electrolyzers through interphase engineering

Anion-exchange membrane water electrolyzers (AEMWEs) promise scalable, low-cost hydrogen production but are limited by the electrochemical instability of their anode ionomers. We report interphase engineering using inorganic-containing molecular additives that coassemble with ionomer, enabling pure water-fed AEMWEs to operate with a degradation rate <0.5 millivolt per hour at 2.0 amperes per square centimeter and 70°C-a >20-fold durability improvement. Analysis of different additives and ionomers shows that the stabilization mechanism involves cross-links between metal oxo/hydroxo oligomers and ionomers. Under operation, the inorganic additive enriches, forming an interphase near the water-oxidation catalyst that passivates the anode ionomer against continuous degradation while maintaining mechanical integrity and hydroxide conductivity. This additive-based interphase-engineering strategy provides a path to durable AEMWEs that operate without supporting electrolytes and is adaptable across diverse catalysts and ionomers for electrochemical technologies.

Hou, Shujin↗
DOE OSTI2022

TiO x -supported Na-Mn-W oxides for the oxidative coupling of methane

Supported Na-Mn-W oxides are among the most studied catalysts for the oxidative coupling of methane (OCM) because of their superior thermal stability and relatively high C 2+ product yields. However, because of the structural complexity, the roles of each component in these catalysts have been controversial. In this work, WO x and MnO x sites were supported on titanate nanowires and employed in OCM studies. Compared to the commonly studied silica support, which is subject to severe restructuring due to the Na-induced crystallization, titanate support not only serves as a reservoir for alkali metals (e.g., Na), but also stabilizes isolated MnO x species. The catalytic performance of the titanate-based catalyst is similar to that of reference catalyst, MnO x /Na 2 WO 4 /SiO 2 , with a synergistic effect between MnO x and WO x sites. Further, advanced electron microscopy, X-ray diffraction, infrared spectroscopy, and X-ray absorption near edge structure spectroscopy suggest that the basic NaO x and MnO x species have strong interactions with the acidic WO x and TiO x species, which might contribute to the high selectivity toward C 2+ products and suppressed CO x formation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗