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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 307 records · Page 17
All sourcesNASA NTRSDOE OSTI
DOE OSTI2014

Correlating the degree of metal–promoter interaction to ethanol selectivity over MnRh/CNTs CO hydrogenation catalysts

Multi-walled carbon nanotubes (MCNTs) were used as a support for Rh-based catalysts for high pressure (20 bar) CO hydrogenation. 3 wt% Rh/CNTs catalysts were loaded with 1 wt% and 2 wt% Mn promoter, respectively, in order to study the effect of metal–promoter interactions for ethanol synthesis. Both STEM and EXAFS results showed ≈1 nm Rh particles in promoted as well as the unpromoted catalysts, STEM and EELS results verified the enhanced metal–promoter interaction when the amount of Mn promoter increased from 1 wt% to 2 wt%. The enhancement in the degree of metal–promoter interaction leads to an increase in the ethanol selectivity. Moreover, due to the nature of CNTs (low Z number), the Mn–Rh interactions could be observed at atomic resolution during the STEM–EELS characterization, and the promoter phase is confirmed as Mn(II) oxide by XANES and EELS.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Selective propane dehydrogenation with single-site Co II on SiO 2 by a non-redox mechanism

We report the synthesis, characterization, and catalytic performance for gas phase propane dehydrogenation of single-site Co2+ ions supported on silica. Spectroscopic characterization by resonance Raman, electron paramagnetic resonance, and X-ray near-edge and extended absorption fine structure revealed that tetrahedrally coordinated Co2+ ions are chemisorbed into the trisiloxane rings on the surface of amorphous silica. In situ XAS shows that Co is not oxidized by air nor reduced by hydrogen even at 650 degrees C. For catalytic propane dehydrogenation, single-site Co2+/SiO2 exhibits selectivities >95% at 550 degrees C and >90% at 650 degrees C with stable activity over 24 h. Calculations with hybrid density functional theory support a non-redox mechanism for activation of C-H and H-H bonds by Co2+ similar to that previously reported for single-site Zn2+/SiO2.

Dehydrogenation↗
DOE OSTI2015

Cytochrome P450 1b1 in polycyclic aromatic hydrocarbon (PAH)-induced skin carcinogenesis: Tumorigenicity of individual PAHs and coal-tar extract, DNA adduction and expression of select genes in the Cyp1b1 knockout mouse

FVB/N mice wild-type, heterozygous or null for Cyp 1b1 were used in a two-stage skin tumor study comparing PAH, benzo[a]pyrene (BaP), dibenzo[def,p]chrysene (DBC), and coal tar extract (CTE, SRM 1597a). Following 20 weeks of promotion with TPA the Cyp 1b1 null mice, initiated with DBC, exhibited reductions in incidence, multiplicity, and progression. None of these effects were observed with BaP or CTE. The mechanism of Cyp 1b1-dependent alteration of DBC skin carcinogenesis was further investigated by determining expression of select genes in skin from DBC-treated mice 2, 4 and 8 h post-initiation. A significant reduction in levels of Cyp 1a1, Nqo1 at 8 h and Akr 1c14 mRNA was observed in Cyp 1b1 null (but not wt or het) mice, whereas no impact was observed in Gst a1, Nqo 1 at 2 and 4 h or Akr 1c19 at any time point. Cyp 1b1 mRNA was not elevated by DBC. The major covalent DNA adducts, dibenzo[def,p]chrysene-(±)-11,12-dihydrodiol-cis and trans-13,14-epoxide-deoxyadenosine (DBCDE-dA) were quantified by UHPLC-MS/MS 8 h post-initiation. Loss of Cyp1 b1 expression reduced DBCDE-dA adducts in the skin but not to a statistically significant degree. The ratio of cis- to trans-DBCDE-dA adducts was higher in the skin than other target tissues such as the spleen, lung and liver (oral dosing). These results document that Cyp 1b1 plays a significant role in bioactivation and carcinogenesis of DBC in a two-stage mouse skin tumor model and that loss of Cyp 1b1 has little impact on tumor response with BaP or CTE as initiators. - Highlights: • Cyp1b1 null mice exhibit lower skin cancer sensitivity to DBC but not BaP or CTE. • Cyp1b1 expression impacts expression of other PAH metabolizing enzymes. • cis/trans-DBCDE-dA ratio significantly higher in the skin than the spleen, lung or liver • Potency of DBC and CTE in mouse skin is higher than predicted by RPFs.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2023

Single-Step Selective Oxidation of Methane by Iron-Oxo Species in the Metal–Organic Framework MFU-4l

The direct and selective conversion of methane to methanol can be considered a holy grail for catalysis research. In this work, we study a metal-organic framework known as MFU-4l, modified by design to include highly reactive iron-oxo species for the catalytic C-H bond activation of methane. We investigate the oxidation of methane and the further potential oxidation of the product methanol using N 2 O as an oxygen source and map the potential energy landscape of these reactions using density functional theory calculations. We show that the highest energy barrier encountered during the methane oxidation process is not the C-H bond breaking, but the activation of the iron center by N 2 O. Furthermore, the potential energy landscape for the C-H bond activation exhibits a large, high-energy plateau region instead of a sharp transition state, thus differing from the traditional radical rebound mechanism. Furthermore, this insight offers interesting potential routes to enhance the catalytic activity of the catalyst, to hinder unwanted deactivation pathways, and to reduce the activity towards the over-oxidation of the product.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Considering a Possible Role for [H-Fe 4 N(CO) 12 ] 2- in Selective Electrocatalytic CO 2 Reduction to Formate by [Fe 4 N(CO) 12 ] -

[Fe 4 N(CO) 12 ] - is a first-row transition element electrocatalyst that selectively produces C–H bonds to give formate from CO 2 in water at -1.2 V vs SCE. We present a thermochemical analysis which probes the possibility that [H-Fe 4 N(CO) 12 ] 2– ((H- 1 ) 2– ) is an intermediate in this process: we show that (H- 1 ) 2– is accessible at -1.2 V vs SCE, but if it were formed, we predict that it would generate H 2 . [Fe 4 N(CO) 12 ] 3– and (H- 1 ) 2– were interrogated spectroscopically, and the product of CO loss, [Fe 4 N(CO) 9 (μ-CO) 2 ] 3– , was synthesized and characterized. Ultimately, we demonstrate that (H- 1 ) 2– is an unlikely participant in the catalytic transformation of CO 2 to formate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Rational Design of a Catalyst for the Selective Monoborylation of Methane

Combined computational and experimental studies elucidate the mechanism and suggest rational design and optimization strategies of a bis(phosphine)-supported iridium-catalyst for methane monoborylation. The activation of the C–H bond in methane via oxidative addition using tris(boryl) iridium(III) complexes bearing bis-chelating supporting ligands is modeled computationally. This model shows that the use of the soft Lewis base ligand such as 1,2-bis(dimethylphosphino)ethane (dmpe) lowers the activation barrier of the rate-determining step as it facilitates polarization of the metal-center, lowering the barrier of the oxidative addition to afford a seven-coordinate iridium(V) intermediate. The experimental optimization of this reaction using high-throughput methods shows that up to 170 turnovers can be achieved at 150 °C (500 psi) within 16 h using bis(pinacolato)diboron, a well-defined homogeneous and monomeric catalyst (dmpe)Ir(COD)Cl that is readily available from commercial precursors, with selectivity for the monoborylation product. High-boiling cyclic aliphatic solvents decalin and cyclooctane also prove suitable for this reaction, while being inert toward borylation. In accordance with the lower calculated activation barrier, catalytic turnover is also observed at 120 °C with up to 50 turnovers over the course of 4 days in cyclohexane solvent. Here, it was found that the borylation of methane is only achieved via one catalytic cycle, and buildup of pinacolborane, a side-product from methane borylation with bis(pinacolato)diboron, inhibits catalytic activity.

computational molecular modeling↗
DOE OSTI2012

Oxidative Dehydrogenation of Cyclohexane on Cobalt Oxide (Co 3 O 4 ) Nanoparticles: The Effect of Particle Size on Activity and Selectivity

The oxidative dehydrogenation of cyclohexane by cobalt oxide nanoparticles was studied via temperature programmed reaction combined with in situ grazing incidence X-ray absorption spectroscopy and grazing incidence small-angle X-ray scattering and theoretical calculations on model Co 3 O 4 substrates. Both 6 and 12 nm Co 3 O 4 nanoparticles were made through a surfactant-free preparation and dispersed on an Al 2 O 3 surface formed by atomic layer deposition. Under reaction conditions the nanoparticles retained their oxidation state and did not sinter. They instead underwent an assembly/disassembly process and could reorganize within their assemblies. The selectivity of the catalyst was found to be size- and temperature-dependent, with larger particles preferentially producing cyclohexene at lower temperatures and smaller particles predominantly resulting in benzene at higher temperatures. The mechanistic features thought to control the oxidative dehydrogenation of cyclohexane and other light alkanes on cobalt oxide were established by carrying out density functional theory calculations on the activation of propane, a surrogate model alkane, over model Co 3 O 4 surfaces. The initial activation of the alkane (propane) proceeds via hydrogen abstraction over surface oxygen sites. The subsequent activation of the resulting alkoxide intermediate occurs at a second surface oxygen site to form the alkene (propene) which then desorbs from the surface. Hydroxyl recombination results in the formation of water which desorbs from the surface. Finally, oxygen is necessary to regenerate the surface oxygen sites, catalyze C–H activation steps, and minimize catalyst degradation.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2021

Selective Photodimerization in a Cyclodextrin Metal–Organic Framework

For the most part, enzymes contain one active site wherein they catalyze in a serial manner chemical reactions between substrates both efficiently and rapidly. Imagine if a situation could be created within a chiral porous crystal containing trillions of active sites where substrates can reside in vast numbers before being converted in parallel into products. Here, we report how it is possible to incorporate 1-anthracenecarboxylate (1-AC – ) as a substrate into a γ-cyclodextrin-containing metal–organic framework (CD-MOF-1), where the metals are K + cations, prior to carrying out [4+4] photodimerizations between pairs of substrate molecules, affording selectively one of four possible regioisomers. One of the high-yielding regioisomers exhibits optical activity as a result of the presence of an 8:1 ratio of the two enantiomers following separation by high-performance liquid chromatography. The solid-state superstructure of 1-anthracenecarboxylate potassium salt (1-ACK), which is co-crystallized with γ-cyclodextrin, reveals that pairs of substrate molecules are not only packed inside tunnels between spherical cavities present in CD-MOF-1, but also stabilized—in addition to hydrogen-bonding to the C-2 and C-3 hydroxyl groups on the d-glucopyranosyl residues present in the γ-cyclodextrin tori—by combinations of hydrophobic and electrostatic interactions between the carboxyl groups in 1-AC– and four K + cations on the waistline between the two γ-cyclodextrin tori in the tunnels. Here, these non-covalent bonding interactions result in preferred co-conformations that account for the highly regio- and enantioselective [4+4] cycloaddition during photoirradiation. Theoretical calculations, in conjunction with crystallography, support the regio- and stereochemical outcome of the photodimerization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Synergistic Effects in Bimetallic Palladium–Copper Catalysts Improve Selectivity in Oxygenate Coupling Reactions

Condensation reactions such as Guerbet and aldol are important since they allow for C-C bond formation and give higher molecular weight oxygenates. An previous study identified Pd-supported on hydrotalcite as an active catalyst for the transformation, although this catalyst showed extensive undesirable decarbonylation. A catalyst containing Pd and Cu in a 3:1 ratio dramatically decreased decarbonylation, while preserving the high catalytic rates seen with Pd-based catalysts. A combination of XRD, EXAFS, TEM, and CO chemisorption and TPD revealed the formation of CuPd bimetallic nanoparticles with a Cu-enriched surface. Finally, density functional theory studies suggest that the surface segregation of Cu atoms in the bimetallic alloy catalyst produces Cu sites with increased reactivity, while the Pd sites responsible for unselective decarbonylation pathways are selectively poisoned by CO.

36 MATERIALS SCIENCE↗