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Title: Catalytic activation of ethylene C–H bonds on uniform d8 Ir(I) and Ni(II) cations in zeolites: toward molecular level understanding of ethylene polymerization on heterogeneous catalysts

Abstract

The homolytic activation of the strong C–H bonds in ethylene is demonstrated, for the first time, on d8 Ir(I) and Ni(II) single atoms in the cationic positions of zeolites H-FAU and H-BEA under ambient conditions. The oxidative addition of C2H4 to the metal center occurs with the formation of a d6 metal vinyl hydride, explaining the initiation of the olefin-polymerization cycle on d8 M(I/II) sites in the absence of pre-existing M–H bonds. Under mild reaction conditions (80–220 °C, 1 bar), the catalytic dimerization to butenes and dehydrogenative coupling of ethylene to butadiene occurs over these catalysts. 1-Butene is not converted to butadiene under the reaction conditions applied. Post-reaction characterization of the two materials reveals that the active metal cations remain site-isolated whereas deactivation occurs due to the formation of carbonaceous deposits on the zeolites. Here, our findings have significant implications for the molecular level understanding of ethylene conversion and the development of new ways to functionalize C–H bonds under mild conditions.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2];  [2]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [2]
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  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Washington State Univ., Pullman, WA (United States)
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
OSTI Identifier:
1577860
Alternate Identifier(s):
OSTI ID: 1571682
Report Number(s):
PNNL-SA-148436
Journal ID: ISSN 2044-4753; CSTAGD
Grant/Contract Number:  
AC05-76RL01830
Resource Type:
Accepted Manuscript
Journal Name:
Catalysis Science and Technology
Additional Journal Information:
Journal Volume: 9; Journal Issue: 23; Journal ID: ISSN 2044-4753
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Jaegers, Nicholas R., Khivantsev, Konstantin, Kovarik, Libor, Klas, Daniel W., Hu, Jian Zhi, Wang, Yong, and Szanyi, János. Catalytic activation of ethylene C–H bonds on uniform d8 Ir(I) and Ni(II) cations in zeolites: toward molecular level understanding of ethylene polymerization on heterogeneous catalysts. United States: N. p., 2019. Web. doi:10.1039/C9CY01442J.
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Jaegers, Nicholas R., Khivantsev, Konstantin, Kovarik, Libor, Klas, Daniel W., Hu, Jian Zhi, Wang, Yong, & Szanyi, János. Catalytic activation of ethylene C–H bonds on uniform d8 Ir(I) and Ni(II) cations in zeolites: toward molecular level understanding of ethylene polymerization on heterogeneous catalysts. United States. https://doi.org/10.1039/C9CY01442J
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Jaegers, Nicholas R., Khivantsev, Konstantin, Kovarik, Libor, Klas, Daniel W., Hu, Jian Zhi, Wang, Yong, and Szanyi, János. Tue . "Catalytic activation of ethylene C–H bonds on uniform d8 Ir(I) and Ni(II) cations in zeolites: toward molecular level understanding of ethylene polymerization on heterogeneous catalysts". United States. https://doi.org/10.1039/C9CY01442J. https://www.osti.gov/servlets/purl/1577860.
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@article{osti_1577860,
title = {Catalytic activation of ethylene C–H bonds on uniform d8 Ir(I) and Ni(II) cations in zeolites: toward molecular level understanding of ethylene polymerization on heterogeneous catalysts},
author = {Jaegers, Nicholas R. and Khivantsev, Konstantin and Kovarik, Libor and Klas, Daniel W. and Hu, Jian Zhi and Wang, Yong and Szanyi, János},
abstractNote = {The homolytic activation of the strong C–H bonds in ethylene is demonstrated, for the first time, on d8 Ir(I) and Ni(II) single atoms in the cationic positions of zeolites H-FAU and H-BEA under ambient conditions. The oxidative addition of C2H4 to the metal center occurs with the formation of a d6 metal vinyl hydride, explaining the initiation of the olefin-polymerization cycle on d8 M(I/II) sites in the absence of pre-existing M–H bonds. Under mild reaction conditions (80–220 °C, 1 bar), the catalytic dimerization to butenes and dehydrogenative coupling of ethylene to butadiene occurs over these catalysts. 1-Butene is not converted to butadiene under the reaction conditions applied. Post-reaction characterization of the two materials reveals that the active metal cations remain site-isolated whereas deactivation occurs due to the formation of carbonaceous deposits on the zeolites. Here, our findings have significant implications for the molecular level understanding of ethylene conversion and the development of new ways to functionalize C–H bonds under mild conditions.},
doi = {10.1039/C9CY01442J},
journal = {Catalysis Science and Technology},
number = 23,
volume = 9,
place = {United States},
year = {2019},
month = {10}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1039/C9CY01442J
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Cited by: 12 works
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Figures / Tables:

Figure 1 Figure 1: A). FTIR during CO adsorption on dry 0.4% Ni/BEA, P(CO)max=5 Torr (the band at 2162 cm-1 represents adsorbed 13CO molecules) B). High-resolution HAADF-STEM image of the 0.4% Ni/BEA material: straight channels in BEA nanocrystals are clearly imaged. No NiO clusters or particles observed (additional HAADF-STEM images provided inmore » Figure S2) C). EDS mapping of Ni, Al, Si, and Ni/Al overlay in 0.4% Ni/BEA.« less
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