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Title: Evidence for Dynamic Chemical Kinetics at Individual Molecular Ruthenium Catalysts

Authors:
 [1]; ORCiD logo [1]
  1. Department of Chemistry, University of California, Irvine, Irvine CA 92697-2025 USA
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1416404
Grant/Contract Number:
SC0016467
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 57; Journal Issue: 6; Related Information: CHORUS Timestamp: 2018-01-31 06:00:21; Journal ID: ISSN 1433-7851
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

Easter, Quinn T., and Blum, Suzanne A. Evidence for Dynamic Chemical Kinetics at Individual Molecular Ruthenium Catalysts. Germany: N. p., 2018. Web. doi:10.1002/anie.201711314.
Easter, Quinn T., & Blum, Suzanne A. Evidence for Dynamic Chemical Kinetics at Individual Molecular Ruthenium Catalysts. Germany. doi:10.1002/anie.201711314.
Easter, Quinn T., and Blum, Suzanne A. 2018. "Evidence for Dynamic Chemical Kinetics at Individual Molecular Ruthenium Catalysts". Germany. doi:10.1002/anie.201711314.
@article{osti_1416404,
title = {Evidence for Dynamic Chemical Kinetics at Individual Molecular Ruthenium Catalysts},
author = {Easter, Quinn T. and Blum, Suzanne A.},
abstractNote = {},
doi = {10.1002/anie.201711314},
journal = {Angewandte Chemie (International Edition)},
number = 6,
volume = 57,
place = {Germany},
year = 2018,
month = 1
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on January 9, 2019
Publisher's Accepted Manuscript

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  • A comparative x-ray-spectroscopic and quantum-chemical investigation of the electronic structure of the complexes (RuL/sub 6/) and (RuL/sub 5/X) (L = NH/sub 3/, CN/sup -/, Cl/sup -/; X = CO, NO, H/sub 2/O) has been conducted. It has been shown that x-ray spectra, which are sensitive to changes in the electron density on the central atom and the ligand, can be used to determine the charges on them. The spectra of oxygen in the NO ligand in the nitrosyl complexes (RuL/sub 5/NO) contains information on the sigma or ..pi.. interactions of the NO group with the metal in accordance with themore » type of the ligand L. The orbital mechanism of the mutual influences of ligands in substituted ruthenium complexes has been analyzed.« less
  • The effects of using D/sub 2/ rather than H/sub 2/ during Fischer-Tropsch synthesis were investigated using alumina- and silica-supported Ru catalysts. For the alumina-supported catalysts, the rate of CD/sub 4/ formation was 1.4 to 1.6 times faster than the formation of CH/sub 4/. A noticeable isotope effect was also observed for higher molecular weight products. The magnitude of the isotope effects observed using the silica-supported catalyst was much smaller than that found using the alumina-supported catalysts. The formation of olefins relative to paraffins was found to be higher when H/sub 2/ rather than D/sub 2/ was used, independent of themore » catalyst support. The observed isotope effects are explained in terms of a mechanism for CO hydrogenation and are shown to arise from a complex combination of the kinetic and equilibrium isotope effects associated with elementary processes occurring on the catalyst surface.« less
  • Fischer-Tropsch synthesis seems to develop the following two consecutive paths: a primary process that involves the formation of {alpha}-olefin products and a secondary process leading to the production of branched isomers and paraffins and requiring the readsorption of primary {alpha}-olefin products. It was already shown by Iglesia et al. that such readsorption steps are of fundamental importance for Ru catalysts and that they occur due to the slow diffusive removal of {alpha}-olefins when the molecular size increases, this resulting in a long intraparticle residence time. In the present paper {alpha}-olefins readsorption was enhanced by changing the metal distribution inside themore » pores of a titanium silicate (ETS-10), modified by ion exchange with alkali metal ions, used as a support for Ru-based catalysts. 24 refs., 5 figs., 3 tabs.« less