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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 343 records · Page 19
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Spin-modified catalysis

First-principle calculations are used to explore the use of magnetic degrees of freedom in catalysis. We use the Vienna Ab-Initio Simulation Package to investigate both L1{sub 0}-ordered FePt and CoPt bulk materials and perform supercell calculations for FePt nanoclusters containing 43 atoms. As the catalytic activity of transition-metal elements and alloys involves individual d levels, magnetic alloying strongly affects the catalytic performance, because it leads to shifts in the local densities of states and to additional peaks due to magnetic-moment formation. The peak shift persists in nanoparticles but is surface-site specific and therefore depends on cluster size. Our research indicates that small modifications in stoichiometry and cluster size are a useful tool in the search for new catalysts.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

On the origin of ground-state vacuum-field catalysis: Equilibrium consideration

Recent experiments suggest that vibrational strong coupling (VSC) may significantly modify ground-state chemical reactions and their rates even without external pumping. The intrinsic mechanism of this “vacuum-field catalysis” remains largely unclear. Generally, modifications of thermal reactions in the ground electronic states can be caused by equilibrium or non-equilibrium effects. The former are associated with modifications of the reactant equilibrium distribution as expressed by the transition state theory of chemical reaction rates, while the latter stem from the dynamics of reaching and leaving transition state configurations. In this work, we examine how VSC can affect chemical reactions rates in a cavity environment according to transition state theory. Our approach is to examine the effect of coupling to cavity mode(s) on the potential of mean force (PMF) associated with the reaction coordinate. Within the context of classical nuclei and classical photons and also assuming no charge overlap between molecules, we find that while the PMF can be affected by the cavity environment, this effect is negligible for the usual micron-length cavities used to examine VSC situations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Protein conformational dynamics in the mechanism of HIV-1 protease catalysis

We have used chemical protein synthesis and advanced physical methods to probe dynamics-function correlations for the HIV-1 protease, an enzyme that has received considerable attention as a target for the treatment of AIDS. Chemical synthesis was used to prepare a series of unique analogues of the HIV-1 protease in which the flexibility of the 'flap' structures (residues 37-61 in each monomer of the homodimeric protein molecule) was systematically varied. These analogue enzymes were further studied by X-ray crystallography, NMR relaxation, and pulse-EPR methods, in conjunction with molecular dynamics simulations. We show that conformational isomerization in the flaps is correlated with structural reorganization of residues in the active site, and that it is preorganization of the active site that is a rate-limiting factor in catalysis.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2019

Hydrophobic catalysis and a potential biological role of DNA unstacking induced by environment effects

Hydrophobic base stacking is a major contributor to DNA double-helix stability. We report the discovery of specific unstacking effects in certain semihydrophobic environments. Water-miscible ethylene glycol ethers are found to modify structure, dynamics, and reactivity of DNA by mechanisms possibly related to a biologically relevant hydrophobic catalysis. Spectroscopic data and optical tweezers experiments show that base-stacking energies are reduced while base-pair hydrogen bonds are strengthened. We propose that a modulated chemical potential of water can promote “longitudinal breathing” and the formation of unstacked holes while base unpairing is suppressed. Flow linear dichroism in 20% diglyme indicates a 20 to 30% decrease in persistence length of DNA, supported by an increased flexibility in single-molecule nanochannel experiments in poly(ethylene glycol). A limited (3 to 6%) hyperchromicity but unaffected circular dichroism is consistent with transient unstacking events while maintaining an overall average B-DNA conformation. Further information about unstacking dynamics is obtained from the binding kinetics of large thread-intercalating ruthenium complexes, indicating that the hydrophobic effect provides a 10 to 100 times increased DNA unstacking frequency and an “open hole” population on the order of 10 –2 compared to 10 –4 in normal aqueous solution. Spontaneous DNA strand exchange catalyzed by poly(ethylene glycol) makes us propose that hydrophobic residues in the L2 loop of recombination enzymes RecA and Rad51 may assist gene recombination via modulation of water activity near the DNA helix by hydrophobic interactions, in the manner described here. We speculate that such hydrophobic interactions may have catalytic roles also in other biological contexts, such as in polymerases.

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

Conserved residue His-257 of Vibrio cholerae flavin transferase ApbE plays a critical role in substrate binding and catalysis

The flavin transferase ApbE plays essential roles in bacterial physiology, covalently incorporating FMN cofactors into numerous respiratory enzymes that use the integrated cofactors as electron carriers. In this work we performed a detailed kinetic and structural characterization of Vibrio cholerae WT ApbE and mutants of the conserved residue His-257, to understand its role in substrate binding and in the catalytic mechanism of this family. Bi-substrate kinetic experiments revealed that ApbE follows a random Bi Bi sequential kinetic mechanism, in which a ternary complex is formed, indicating that both substrates must be bound to the enzyme for the reaction to proceed. Steady-state kinetic analyses show that the turnover rates of His-257 mutants are significantly smaller than those of WT ApbE, and have increased K m values for both substrates, indicating that the His-257 residue plays important roles in catalysis and in enzyme-substrate complex formation. Analyses of the pH dependence of ApbE activity indicate that the p K a of the catalytic residue (p K ES1 ) increases by 2 pH units in the His-257 mutants, suggesting that this residue plays a role in substrate deprotonation. The crystal structures of WT ApbE and an H257G mutant were determined at 1.61 and 1.92 Å resolutions, revealing that His-257 is located in the catalytic site and that the substitution does not produce major conformational changes. In this paper, we propose a reaction mechanism in which His-257 acts as a general base that deprotonates the acceptor residue, which subsequently performs a nucleophilic attack on FAD for flavin transfer.

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

A requirement for an active proton delivery network supports a compound I-mediated C–C bond cleavage in CYP51 catalysis

CYP51 enzymes (sterol 14α-demethylases) are cytochromes P450 that catalyze multistep reactions. The CYP51 reaction occurs in all biological kingdoms and is essential in sterol biosynthesis. It removes the 14α-methyl group from cyclized sterol precursors by first forming an alcohol, then an aldehyde, and finally eliminating formic acid with the introduction of a Δ14–15 double bond in the sterol core. The first two steps are typical hydroxylations, mediated by an electrophilic compound I mechanism. The third step, C–C bond cleavage, has been proposed to involve either compound I (i.e. FeO 3+ ) or, alternatively, a proton transfer-independent nucleophilic ferric peroxo anion (compound 0, i.e. Fe 3+ O 2 – ). In this work, using comparative crystallographic and biochemical analyses of WT human CYP51 (CYP51A1) and its D231A/H314A mutant, whose proton delivery network is destroyed (as evidenced in a 1.98-Å X-ray structure in complex with lanosterol), we demonstrate that deformylation of the 14α-carboxaldehyde intermediate requires an active proton relay network to drive the catalysis. These results indicate a unified, compound I-based mechanism for all three steps of the CYP51 reaction, as previously established for CYP11A1 and CYP19A1. We anticipate that our approach can be applied to mechanistic studies of other P450s that catalyze multistep reactions, such as C–C bond cleavage.

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

Availability and reactivity of N 2 ( v ) for NH 3 synthesis by plasma catalysis

Production of vibrationally excited N 2 (N 2 (v)) in atmospheric pressure nonthermal plasma and loss of N 2 (v) by gas-phase reactions and reactions on catalytic surfaces are analyzed to examine the role of N 2 (v) in NH 3 formation by plasma catalysis. Vibrational state-to-state kinetic models complemented with molecular beam mass spectrometry (MBMS) measurements demonstrate that N 2 (v> 0) is produced with densities 100× greater than the density of N radicals by a radiofrequency atmospheric pressure plasma jet. The experimentally measured loss of N 2 (v) corresponds with a state-to-state kinetic model that describes loss of N 2 (v) by surface-mediated vibrational relaxation without consideration of reactions that convert N 2 (v) to NH 3 over the catalyst surface. Rate constants for vibrational relaxation of N 2 (v) on catalyst surfaces exceed upper bounds on proposed rate constants for NH 3 formation reactions from N 2 (v) over Fe when v < 9, Ni when v < 18, and Ag when v < 39, which indicates that only higher vibrational levels can possibly contribute to catalytic NH 3 formation faster than they undergo vibrational relaxation on the surface. Densities of N 2 (v> 8), vibrational levels that can possibly react over Fe to form NH 3 faster than they undergo vibrational relaxation, are less than or similar to N densities at the inlet of the catalyst bed and measured NH 3 formation for the investigated conditions in this work, while densities of N 2 (v> 17) and N 2 (v> 38) are orders of magnitude below the N density at the inlet of the catalyst bed and the measured NH 3 formation. The loss of N 2 (v) by vibrational relaxation on the surface limits the ability of N 2 (v) to contribute to catalytic NH 3 formation and explains why N 2 (v) does not produce NH 3 in quantities that are comparable to NH 3 formation from N even though N 2 (v > 0) is more abundantly produced by the plasma.

state-to-state kinetic modeling↗
DOE OSTI2016

Physical applications of muon catalysis: Muon capture in hydrogen

Results: of theoretical and experimental research on capture of negative muons in hydrogen are reported with an emphasis on the accompanying phenomenon of muon catalysis in hydrogen and subtleties of the experimental method. A conclusion is drawn that precise determination of the capture rate is important for refining the standard model.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2024

Chiral catalysis of nuclear fusion in molecules

At low energies, nuclear fusion is strongly affected by electron screening of the Coulomb repulsion among the fusing nuclei. It may thus be possible to catalyze nuclear fusion in molecules (i.e., to fuse specific nuclei in situ) through quantum control of electron wave functions in intense laser fields. The circularly polarized (chiral) laser field can effectively squeeze the electron wave functions, greatly enhancing the screening in the spatial region relevant for the fusion process. Here, we estimate the corresponding fusion probabilities, and find that the proposed chiral catalysis of nuclear fusion in molecules may be observable, potentially with important practical applications.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2025

Ultrafast Spectroscopy and Dynamics of Photoredox Catalysis

Photoredox catalysis has emerged as a powerful platform for chemical synthesis, utilizing chromophore excited states as selective energy stores to surmount chemical activation barriers toward making desirable products. Developments in this field have pushed synthetic chemists to design and discover new photocatalysts with novel and impactful photoreactivity but also with uncharacterized excited states and only an approximate mechanistic understanding. This review highlights specific instances in which ultrafast spectroscopies dissected the photophysical and photochemical dynamics of new classes of photoredox catalysts and their photochemical reactions. After briefly introducing the photophysical processes and ultrafast spectroscopic methods central to this topic, the review describes selected recent examples that evoke distinct classes of photoredox catalysts with demonstrated synthetic utility and ultrafast spectroscopic characterization. Furthermore, this review cements the significant role of ultrafast spectroscopy in modern photocatalyzed organic transformations and institutionalizes the developing intersection of synthetic organic chemistry and physical chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

High-Spin Cobalt Hydrides for Catalysis

Organometallic chemists have traditionally used catalysts with strong-field ligands that give low-spin complexes. However, complexes with a weak ligand field have weaker bonds and lower barriers to geometric changes, suggesting that they may lead to more rapid catalytic reactions. Developing our understanding of high-spin complexes requires the use of a broader range of spectroscopic techniques, but has the promise of changing the mechanism and/or selectivity of known catalytic reactions. These changes may enable the more efficient utilization of chemical resources. A special advantage of cobalt and iron catalysts is that the metals are more abundant and cheaper than those currently used for major industrial processes that convert unsaturated organic molecules and biofeedstocks into useful chemicals. This project specifically evaluated the potential of high-spin cobalt complexes for small-molecule reactions for bond rearrangement and cleavage reactions relevant to hydrocarbon transformations. We have learned that many of these reactions proceed through crossing to different spin states: for example, high-spin complexes can flip one electron spin to access a lower-energy reaction pathway for beta-hydride elimination. This reaction enables new, selective olefin isomerization catalysis. The high-spin cobalt complexes also cleave the C-O bond of CO2 and the C-F bonds of fluoroarenes. In each case, the detailed mechanism of the reaction has been determined. Importantly, we have discovered that the cobalt catalysts described here give distinctive selectivities that are better than known catalysts. These selectivities come from a synergy between supporting ligand design and electronic control of the spin-state crossing in the reactions.

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

Predictive Modeling in Actinide Chemistry and Catalysis

These are slides from a presentation on predictive modeling in actinide chemistry and catalysis. The following topics are covered in these slides: Structures, bonding, and reactivity (bonding can be quantified by optical probes and theory, and electronic structures and reaction mechanisms of actinide complexes); Magnetic resonance properties (transition metal catalysts with multi-nuclear centers, and NMR/EPR parameters); Moving to more complex systems (surface chemistry of nanomaterials, and interactions of ligands with nanoparticles); Path forward and conclusions.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2022

Step Catalysis to Synthesize Fossil-Free Ammonia at Atmospheric Pressure (Final Technical Report)

Affordable fossil-free ammonia synthesis will enable high-yield sustainable crop production for a growing world population while preserving the planet and making the best use of water and land. Simple technology amenable to intermittent operation using renewable energy will be made available through step catalysis activating dinitrogen at atmospheric pressure by nitride formation. Project objectives: (1) At the single particle level, quantify and analyze N2 activation by doped or alloyed manganese macroscopic- and nano particles at atmospheric pressure, (2) Quantify and analyze ammonia synthesis from doped or alloyed metal nitride particles when contacting them with hydrogen at atmospheric pressure, and (3) Integrate experimental data and atomic-level computational models to predict the behavior of metal alloys in nitrogen activation and subsequent ammonia synthesis.

10 SYNTHETIC FUELS↗
DOE OSTI2024

EFRC Accomplishments: Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC)

The vision of IMASC is to advance the fundamental science necessary to alter fundamental aspects of the chemical industries sector and its carbon footprint. The IMASC mission is to develop design principles for increasing the efficiency of key chemical syntheses using dilute alloy catalysts by quantitatively scaling from model studies to catalytic operation using advanced experiment and theory. One of the major challenges in catalysis is predicting catalytic behavior—especially selectivity. The IMASC team developed a methodology for obtaining critical information for selected catalytic processes using dilute alloy catalysts, that is widely applicable to modeling catalytic processes.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Beyond Pristine Metal–Organic Frameworks: Preparation of Hollow MOFs and Their Composites for Catalysis, Sensing, and Adsorption Removal Applications

Metal–organic frameworks (MOFs) have been broadly applied to numerous domains with a substantial surface area, tunable pore size, and multiple unsaturated metal sites. Recently, hollow MOFs have greatly attracted the scientific community due to their internal cavities and gradient pore structures. Hollow MOFs have a higher tunability, faster mass-transfer rates, and more accessible active sites when compared to traditional, solid MOFs. Hollow MOFs are also considered to be candidates for some functional material carriers. For example, composite materials such as hollow MOFs and metal nanoparticles, metal oxides, and enzymes have been prepared. These composite materials integrate the characteristics of hollow MOFs with functional materials and are broadly used in many aspects. This review describes the preparation strategies of hollow MOFs and their composites as well as their applications in organic catalysis, electrochemical sensing, and adsorption separation. Finally, we hope that this review provides meaningful knowledge about hollow-MOF composites and their derivatives and offers many valuable references to develop hollow-MOF-based applied materials.

36 MATERIALS SCIENCE↗