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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 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

On the Limited Role of Electronic Support Effects in Selective Alkyne Hydrogenation: A Kinetic Study of Au/MO x Catalysts Prepared from Oleylamine‐Capped Colloidal Nanoparticles

Abstract We report a quantitative kinetic evaluation and study of support effects for partial alkyne hydrogenation using oleylamine‐capped Au colloids as catalyst precursors. The amine capping agents can be removed under reducing conditions, generating supported Au nanoparticles of ∼2.5 nm in diameter. The catalysts showed high alkene selectivity (>90 %) at all conversions during alkyne partial hydrogenation. Catalytic activity, observed rate constants, and apparent activation energies (25–40 kJ/mol) were similar for all Au catalysts, indicating support effects are relatively small. Alkyne adsorption, probed with FTIR and DFT, showed adsorption on the support was associated with hydrogen‐bonding interactions. DFT calculations indicate strong alkyne adsorption on Au sites, with the strongest adsorption sites at the metal‐support interface (MSI). The catalysts had similar hydrogen reaction orders (0.7–0.9), and 1‐octyne reaction orders (∼−0.2), suggesting a common mechanism. The reaction kinetics are most consistent with a mechanism involving the non‐competitive activated adsorption of H 2 on an alkyne‐covered Au surface.

Bruno, James E.↗
DOE OSTI2020

Ni5Ga3 Catalysts for CO2 Reduction to Methanol: Exploring the Role of Ga Surface Oxidation/reductions on Catalytic Activity

Ad-Ni5Ga3/SiO2 catalyst, which is highly active and stable for thermal CO2 hydrogenation to methanol, was investigated to understand its surface dynamics during reaction conditions. The catalyst was prepared, tested and characterized using a multitude of techniques, including ex-situ XRD, TEM, H2-TPR, CO chemisorption and in-situ ETEM and APXPS. The formation of Ga2O3 upon air exposure was observed and the consequences on catalytic activity were investigated. Results revealed that upon air exposure Ga migrates from the subsurface region to the surface of the nanoparticles forming a Ga-oxide shell surrounding a metallic core. The oxide shell can be reduced completely at high temperatures and the temperature of the reduction activation treatment plays a crucial role on the catalytic activity. This air exposure-reduction procedure results in a redistribution of the Ga species in the surface/subsurface region, promoted by a higher Ga affinity for oxygen. XRD analysis of the post-reaction samples provide evidence for the partial transformation of a Ni5Ga3 intermetallic phase into a Ni-rich Ni3Ga phase. APXPS data indicate that the Ni-rich phase forms in the subsurface region. A Ga-rich phase exists on the surface, where the Ni/Ga ratio reaches 2/3 upon activation in hydrogen. At low reduction temperatures an amorphous Ga2O3 shell remains, indicating a promotion effect on methanol synthesis activity.

Ni-Ga, intermetallic, methanol synthesis, in-situ ↗
DOE OSTI2018

Hydrogenation of Diesters on Copper Catalyst Anchored on Ordered Hierarchical Porous Silica: Pore size effect

An ordered hierarchically porous silica (HPS) with the coexistence of both mesopores and abundant micropores was fabricated and used as support for the preparation of copper-based catalysts (Cu/HPS). The ordered mesoporous structure of the Cu/HPS catalysts was retained. In addition, both Cu0 and Cu+ species are found to be highly dispersed. It might be attributed to the anchoring effect of micropores and the formation of Cu-O-Si species derived from the strong interaction between surface silica and copper precursor. The Cu/HPS catalysts showed excellent performances in the hydrogenation of dimethyl adipate. The catalytic activity in dimethyl oxalate hydrogenation depended on the surface reaction, while the activity in dimethyl adipate hydrogenation will be readily controlled by pore diffusion, which can be improved by tailoring the pore size of HPS. These findings could be meaningful instruction for the rational design of industrial catalysts for the hydrogenation of various diesters.

ester, hydrogenation, higherarchical, copper, diff↗
DOE OSTI2018

In Situ Characterization of Mesoporous Co/CeO 2 Catalysts for the High-Temperature Water-Gas Shift

Here, mesoporous Co/CeO 2 catalysts were found to exhibit significant activity for the high-temperature water-gas shift (WGS) reaction with cobalt loadings as low as 1 wt %. The catalysts feature a uniform dispersion of cobalt within the CeO 2 fluorite type lattice with no evidence of discrete cobalt phase segregation. In situ XANES and ambient pressure XPS experiments were used to elucidate the active state of the catalysts as partially reduced cerium oxide doped with oxidized cobalt atoms. In situ XRD and DRIFTS experiments suggest facile cerium reduction and oxygen vacancy formation, particularly with lower cobalt loadings. In situ DRIFTS analysis also revealed the presence of surface carbonate and bidentate formate species under reaction conditions, which may be associated with additional mechanistic pathways for the WGS reaction. Deactivation behavior was observed with higher cobalt loadings. XANES data suggest the formation of small metallic cobalt clusters at temperatures above 400 °C may be responsible. Notably, this deactivation was not observed for the 1% cobalt loaded catalyst, which exhibited the highest activity per unit of cobalt.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Stabilizing High Metal Loadings of Thermally Stable Platinum Single Atoms on an Industrial Catalyst Support

Single atom catalysts have attracted attention because of improved atom efficiency, higher reactivity, and better selectivity. A major challenge is to achieve high surface concentrations while preventing these atoms from agglomeration at elevated temperatures. Here we investigate the formation of Pt single atoms on an industrial catalyst support. Using a combination of surface sensitive techniques such as XPS and LEIS, X-ray absorption spectroscopy, electron microscopy, as well as density functional theory, we demonstrate that cerium oxide can support Pt single atoms at high metal loading (3 wt% Pt), without forming any clusters or 3D aggregates when heated in air at 800 °C. The mechanism of trapping involves a reaction of the mobile PtO2 with under-coordinated cerium cations present at CeO2(111) step edges, allowing Pt to achieve a stable square planar configuration. The strong interaction of mobile single atom species with the support, present during catalyst sintering and regeneration, helps explain the sinter-resistance of ceria-supported metal catalysts.

Kunwar, Deepak↗
DOE OSTI2019

Single-Polymer–Particle Growth Kinetics with Molecular Catalyst Speciation and Single-Turnover Imaging

The dynamics of the local environments surrounding molecular polymerization catalysts plausibly impact turnover kinetics, but the impact of and nature of such dynamics have previously been obscured by ensemble averaging. With Grubbs’ second generation ruthenium metathesis catalyst and a precipitation polymerization system, studies at the single-particle and -turnover level establish that (1) an inverse correlation exists between rate and duration of single-polymer–particle growth of aggregates, consistent with a local environment density model for the time-variable kinetics; (2) cross-linking additives produced a small, but detectible, reduction in overall monomer incorporation; (3) total ruthenium quantity within the polymer particles (as characterized by energy dispersive X-ray spectroscopy) is differentiable from the quantity that is catalytically active (as characterized by in situ fluorescence microscopy), providing catalyst speciation information; and (4) time-resolved enyne metathesis reactions can be imaged, corresponding to single turnovers at individual molecular catalysts during polymer growth under synthetically relevant conditions. Here, these findings identify and characterize reactivity distributions likely arising from the dynamics of local environments. As such, these data provide reactivity information that is unavailable through traditional ensemble analytical methods that obscure this type of information through averaging.

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

Kinetics and Reaction Mechanisms of Acetic Acid Hydrodeoxygenation over Pt and Pt–Mo Catalysts

In this work, kinetic measurements for silica-supported Pt and Pt-Mo catalysts were collected in vapor-phase acetic acid hydrodeoxygenation by varying the hydrogen partial pressure between 18 and 72 kPa and acetic acid partial pressure between 7 and 18 kPa at 423-473 K. At all testing conditions, the Pt-Mo catalyst was more active and selective. In addition, the apparent activation energy for Pt-Mo of 76±3 kJ/mol was lower than that of 84±4 kJ/mol for Pt. The apparent reaction orders were also different. The order in hydrogen of 0.8±0.1 for Pt-Mo changed to zero at higher hydrogen partial pressures while that for Pt remained constant at 0.6±0.1. A near-zero order in acetic acid for Pt-Mo changed to -2.1 at higher acetic acid pressures while that for Pt remained constant at -2.9±0.3. These differences in reaction kinetics as well as in selectivity trends with changes in temperature and feed composition indicated a change in the reaction mechanism for Pt-Mo. The catalysts were characterized with hydrogen temperature programmed desorption, oxygen temperature programmed oxidation and transmission electron microscopy with energy-dispersed X-ray spectroscopy elemental mapping. Mo was present in the form of subnanometer-size clusters on the surface of Pt nanoparticles. Both Pt and Pt-Mo catalysts were stable under the reaction conditions for 10 h, and the size and structure of Pt and Pt-Mo particles remained mostly unchanged, without coke accumulation. Density functional theory calculations show that surface acetate is not a major reaction intermediate on both Pt and Pt-Mo and, instead, C-OH bond splitting with the formation of acetyl is the first reaction step in hydrodeoxygenation. The activation energy for this step is dramatically lower on Pt-Mo. Furthermore, the activity of acetyl on Pt-Mo is different. Unlike on pure Pt, the reaction of C-O bond splitting becomes exothermic with a lower activation energy on Pt-Mo, and the reaction of C-C bond splitting, in contrast, becomes endothermic with a higher activation energy, explaining the experimentally observed higher activities and selectivities of Pt-Mo. In addition, the calculations demonstrate that a pair of Pt-Mo surface atoms acts as a single active site where Mo serves as a preferential binding anchor for O atoms. The presence of Mo atoms changes the structure and energy of adsorbed and reacting surface species.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Self-Assembled Bilayers as an Anchoring Strategy: Catalysts, Chromophores, and Chromophore-Catalyst Assemblies

Anchoring strategies for immobilization of molecular catalysts, chromophores, and chromophore-catalyst assemblies on electrode surfaces play an important role in solar energy conversion devices such as dye-sensitized solar cells and dye-sensitized photoelectrosynthesis cells. They are also important in interfacial studies with surface-bound molecules including electron-transfer dynamics and mechanistic studies related to small molecule activation catalysis. Significant progress has been made in this area, but many challenges remain in terms of stability, synthetic complexity, and versatility. We report here a new anchoring strategy based on self-assembled bilayers. This strategy takes advantage of noncovalent interactions between long alkyl chains chemically bound to a metal-oxide electrode surface and long alkyl chains on the molecule being anchored. Here, the new methodology is applicable to the heterogenization of both catalysts and chromophores as well as to the in situ “synthesis” of chromophore-catalyst assemblies on the electrode surface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗