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dc.contributor.author
Berkson, Zachariah J.
dc.contributor.author
Bernhardt, Moritz
dc.contributor.author
Schlapansky, Simon Laurenz
dc.contributor.author
Benedikter, Mathis J.
dc.contributor.author
Buchmeiser, Michael R.
dc.contributor.author
Price, Gregory A.
dc.contributor.author
Sunley, Glenn J.
dc.contributor.author
Copéret, Christophe
dc.date.accessioned
2022-06-22T06:55:15Z
dc.date.available
2022-05-13T02:45:57Z
dc.date.available
2022-06-22T06:55:15Z
dc.date.issued
2022-03-28
dc.identifier.issn
2691-3704
dc.identifier.other
10.1021/jacsau.2c00052
en_US
dc.identifier.uri
http://hdl.handle.net/20.500.11850/546950
dc.identifier.doi
10.3929/ethz-b-000546950
dc.description.abstract
Molecularly defined and classical heterogeneous Mo-based metathesis catalysts are shown to display distinct and unexpected reactivity patterns for the metathesis of long-chain α-olefins at low temperatures (<100 °C). Catalysts based on supported Mo oxo species, whether prepared via wet impregnation or surface organometallic chemistry (SOMC), exhibit strong activity dependencies on the α-olefin chain length, with slower reaction rates for longer substrate chain lengths. In contrast, molecular and supported Mo alkylidenes are highly active and do not display such dramatic dependence on the chain length. State-of-the-art two-dimensional (2D) solid-state nuclear magnetic resonance (NMR) spectroscopy analyses of postmetathesis catalysts, complemented by Fourier transform infrared (FT-IR) spectroscopy and molecular dynamics calculations, evidence that the activity decrease observed for supported Mo oxo catalysts relates to the strong adsorption of internal olefin metathesis products because of interactions with surface Si–OH groups. Overall, this study shows that in addition to the nature and the number of active sites, the metathesis rates and the overall catalytic performance depend on product desorption, even in the liquid phase with nonpolar substrates. This study further highlights the role of the support and active site composition and dynamics on activity as well as the need for considering adsorption in catalyst design.
en_US
dc.format
application/pdf
en_US
dc.language.iso
en
en_US
dc.publisher
American Chemical Society
en_US
dc.rights.uri
http://creativecommons.org/licenses/by/4.0/
dc.subject
heterogeneous catalysis
en_US
dc.subject
molybdenum
en_US
dc.subject
olefin metathesis
en_US
dc.subject
spectroscopy
en_US
dc.subject
solid-state NMR
en_US
dc.subject
surface organometallic chemistry
en_US
dc.subject
molecular dynamics
en_US
dc.title
Olefin-Surface Interactions: A Key Activity Parameter in Silica-Supported Olefin Metathesis Catalysts
en_US
dc.type
Journal Article
dc.rights.license
Creative Commons Attribution 4.0 International
dc.date.published
2022-03-09
ethz.journal.title
JACS Au
ethz.journal.volume
2
en_US
ethz.journal.issue
3
en_US
ethz.journal.abbreviated
JACS Au
ethz.pages.start
777
en_US
ethz.pages.end
786
en_US
ethz.version.deposit
publishedVersion
en_US
ethz.grant
Predictive design in heterogeneous catalysis through machine learning and surface organometallic chemistry
en_US
ethz.grant
Magnetic Layered Materials from Single Molecular Magnets
en_US
ethz.identifier.wos
ethz.identifier.scopus
ethz.publication.place
Washington, DC
en_US
ethz.publication.status
published
en_US
ethz.leitzahl
ETH Zürich::00002 - ETH Zürich::00012 - Lehre und Forschung::00007 - Departemente::02020 - Dep. Chemie und Angewandte Biowiss. / Dep. of Chemistry and Applied Biosc.::02513 - Laboratorium für Anorganische Chemie / Laboratory of Inorganic Chemistry::03872 - Copéret, Christophe / Copéret, Christophe
ethz.leitzahl.certified
ETH Zürich::00002 - ETH Zürich::00012 - Lehre und Forschung::00007 - Departemente::02020 - Dep. Chemie und Angewandte Biowiss. / Dep. of Chemistry and Applied Biosc.::02513 - Laboratorium für Anorganische Chemie / Laboratory of Inorganic Chemistry::03872 - Copéret, Christophe / Copéret, Christophe
ethz.grant.agreementno
190322
ethz.grant.agreementno
ETH-44 18-1
ethz.grant.fundername
SNF
ethz.grant.fundername
ETHZ
ethz.grant.funderDoi
10.13039/501100001711
ethz.grant.funderDoi
10.13039/501100003006
ethz.grant.program
Spark
ethz.grant.program
ETH Grants
ethz.date.deposited
2022-05-13T02:46:09Z
ethz.source
WOS
ethz.eth
yes
en_US
ethz.availability
Open access
en_US
ethz.rosetta.installDate
2022-06-22T06:55:22Z
ethz.rosetta.lastUpdated
2023-02-07T03:41:03Z
ethz.rosetta.versionExported
true
ethz.COinS
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