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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

Journal Article · · Catalysis Science and Technology
DOI:https://doi.org/10.1039/C9CY01442J· OSTI ID:1577860
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2];  [2]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [2]
  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)
+ Show Author Affiliations

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.

Research Organization:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Organization:
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
Grant/Contract Number:
AC05-76RL01830
OSTI ID:
1577860
Alternate ID(s):
OSTI ID: 1571682
Report Number(s):
PNNL-SA-148436; CSTAGD
Journal Information:
Catalysis Science and Technology, Vol. 9, Issue 23; ISSN 2044-4753
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 12 works
Citation information provided by
Web of Science

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