Olefin oligomerization by main group Ga3+ and Zn2+ single site catalysts on SiO2

LiBretto, Nicole J.; Xu, Yinan; Quigley, Aubrey; Edwards, Ethan; Nargund, Rhea; Vega-Vila, Juan Carlos; Caulkins, Richard; Saxena, Arunima; Gounder, Rajamani; Greeley, Jeffrey; Zhang, Guanghui; Miller, Jeffrey T.

doi:10.1038/s41467-021-22512-6

Olefin oligomerization by main group Ga³⁺ and Zn²⁺ single site catalysts on SiO₂

Journal Article · Mon Apr 19 00:00:00 EDT 2021 · Nature Communications

DOI:https://doi.org/10.1038/s41467-021-22512-6· OSTI ID:1787765

^[1]; ^[1]; Quigley, Aubrey ^[1]; ^[1]; Nargund, Rhea ^[1]; Vega-Vila, Juan Carlos ^[1]; Caulkins, Richard ^[1]; Saxena, Arunima ^[1]; ^[1]; Greeley, Jeffrey ^[1]; ^[2]; ^[1]

Purdue Univ., West Lafayette, IN (United States). Davidson School of Chemical Engineering
Purdue Univ., West Lafayette, IN (United States). Davidson School of Chemical Engineering; Dalian Univ. of Technology (China). State Key Lab. of Fine Chemicals. PSU-DUT Joint Center for Energy Research. School of Chemical Engineering

In heterogeneous catalysis, olefin oligomerization is typically performed on immobilized transition metal ions, such as Ni²⁺ and Cr³⁺. Here we report that silica-supported, single site catalysts containing immobilized, main group Zn²⁺ and Ga³⁺ ion sites catalyze ethylene and propylene oligomerization to an equilibrium distribution of linear olefins with rates similar to that of Ni²⁺. The molecular weight distribution of products formed on Zn²⁺ is similar to Ni²⁺, while Ga³⁺ forms higher molecular weight olefins. In situ spectroscopic and computational studies suggest that oligomerization unexpectedly occurs by the Cossee-Arlman mechanism via metal hydride and metal alkyl intermediates formed during olefin insertion and β-hydride elimination elementary steps. Initiation of the catalytic cycle is proposed to occur by heterolytic C-H dissociation of ethylene, which occurs at about 250 °C where oligomerization is catalytically relevant. This work illuminates new chemistry for main group metal catalysts with potential for development of new oligomerization processes.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1787765

Journal Information:: Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 12; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: ENGLISH

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Olefin oligomerization by main group Ga3+ and Zn2+ single site catalysts on SiO2

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