Olefin-Surface Interactions: A Key Activity Parameter in Silica-Supported Olefin Metathesis Catalysts
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Date
2022-03-28
Publication Type
Journal Article
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yes
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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.
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published
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2 (3)
Pages / Article No.
777 - 786
Publisher
American Chemical Society
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Subject
heterogeneous catalysis; molybdenum; olefin metathesis; spectroscopy; solid-state NMR; surface organometallic chemistry; molecular dynamics
Organisational unit
03872 - Copéret, Christophe / Copéret, Christophe
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Funding
190322 - Predictive design in heterogeneous catalysis through machine learning and surface organometallic chemistry (SNF)
ETH-44 18-1 - Magnetic Layered Materials from Single Molecular Magnets (ETHZ)
ETH-44 18-1 - Magnetic Layered Materials from Single Molecular Magnets (ETHZ)