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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 Cossee-Arlman cycle on d8 M(I/II) sites in the absence of preexisting 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-1 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. 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:
 [1];  [1];  [1];  [1]; ORCiD logo [1];  [2];  [1]
  1. BATTELLE (PACIFIC NW LAB)
  2. WASHINGTON STATE UNIV
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1577860
Report Number(s):
PNNL-SA-148436
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Catalysis Science & Technology
Additional Journal Information:
Journal Issue: 9
Country of Publication:
United States
Language:
English

Citation Formats

Jaegers, Nicholas R., Khivantsev, Konstantin, Kovarik, Libor, Klas, Daniel W., Hu, Jian Z., Wang, Yong, and Szanyi, Janos. 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.
Jaegers, Nicholas R., Khivantsev, Konstantin, Kovarik, Libor, Klas, Daniel W., Hu, Jian Z., Wang, Yong, & Szanyi, Janos. 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. doi:10.1039/C9CY01442J.
Jaegers, Nicholas R., Khivantsev, Konstantin, Kovarik, Libor, Klas, Daniel W., Hu, Jian Z., Wang, Yong, and Szanyi, Janos. Mon . "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. doi:10.1039/C9CY01442J.
@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 Z. and Wang, Yong and Szanyi, Janos},
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 Cossee-Arlman cycle on d8 M(I/II) sites in the absence of preexisting 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-1 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. 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 & Technology},
number = 9,
volume = ,
place = {United States},
year = {2019},
month = {11}
}

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