Catalytic descriptors and electronic properties of single-site catalysts for ethene dimerization to 1-butene

Steven Pellizzeri; Melissa Barona; Varinia Bernales; Pere Miró; Peilin Liao; Laura Gagliardi; Randall Q. Snurr; Rachel B. Getman

doi:10.1016/j.cattod.2018.02.024

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Catalytic descriptors and electronic properties of single-site catalysts for ethene dimerization to 1-butene

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Catalytic descriptors and electronic properties of single-site catalysts for ethene dimerization to 1-butene

Steven Pellizzeri, Melissa Barona, Varinia Bernales, Pere Miró, Peilin Liao, Laura Gagliardi, Randall Q. Snurr and Rachel B. Getman

Catalysis today, Vol.312(C), pp.149-157

08/15/2018

DOI: 10.1016/j.cattod.2018.02.024

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Abstract

[Display omitted] •Single metal cation catalysts were studied for ethene conversion to 1-butene.•Catalysts were supported on 1 the MOF NU-1000 and 2 any material with isolated hydroxyl groups.•Catalysts based on Fe, Ni, Co, and Cu were found to be significantly active. Six first-row transition metal cations (Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Zn2+) were evaluated as catalysts for ethene dimerization to 1-butene. This is an important reaction in the chemistry of CC bond formation and in the conversion of natural gas to higher hydrocarbons. Two related classes of transition metal cation catalysts were investigated: 1) single transition metal cations supported on zirconium oxide nodes of the metal–organic framework NU-1000 and 2) small metal hydroxide clusters with two metal atoms (M2) that could be grown by atomic layer deposition on a support exhibiting isolated hydroxyl groups. Using scaling relations, the free energies of co-adsorbed hydrogen and ethene (i.e., (H/C2H4)*) and adsorbed ethyl (i.e., C2H5*) were identified as descriptors for ethene dimerization catalysis. Using degree of rate control analysis, it was determined that the rate controlling steps are either ethene insertion (CC bond forming) or β-hydride elimination (CH bond breaking), depending on the metal. Using degree of catalyst control analysis, it was determined that activity on all the catalysts studied could be improved by tuning the free energy of C2H5*.

Atomically dispersed catalyst

Computational catalysis

Hydrocarbon chemistry

Metal-organic framework

Microkinetic modeling

Single atom catalyst

Details

Title: Subtitle: Catalytic descriptors and electronic properties of single-site catalysts for ethene dimerization to 1-butene
Creators: Steven Pellizzeri - Clemson University
Melissa Barona - Northwestern University
Varinia Bernales - University of Minnesota
Pere Miró - Northwestern University
Peilin Liao - Northwestern University
Laura Gagliardi - University of Minnesota
Randall Q. Snurr - Northwestern University
Rachel B. Getman - Clemson University
Resource Type: Journal article
Publication Details: Catalysis today, Vol.312(C), pp.149-157
Publisher: Elsevier B.V
DOI: 10.1016/j.cattod.2018.02.024
ISSN: 0920-5861
eISSN: 1873-4308
Grant note: DOI: 10.13039/100006151, name: U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences (BES), award: DE-SC0012702; DOI: 10.13039/100006132, name: Office of Science of the U.S. Department of Energy, award: DE-AC02-05CH11231
Language: English
Date published: 08/15/2018
Academic Unit: Chemistry
Record Identifier: 9984618505202771

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