Selective ethylene dimerization by a nickel-exchanged metal-organic framework catalyst

Short linear [alpha]-olefins such as 1-butene are valuable commodity chemicals due to their use as comonomers in linear low-density polyethylene. Presently only homogeneous systems are used to catalyze ethylene dimerization in industry, causing many to suffer from quick deactivation and poor selectivity. The metal-organic framework (MOF) CPF-5 Mn₅(TBA)₃(HCOO)₃(OH)(H₂O₂)2]]₄·6DMF where TBA = 4-(l H-tetrazol-5-yl)benzoic acid provides an ideal structural template for the development of a heterogeneous catalyst for ethylene dimerization. Ni exchanged CPF-5 (Ni-CPF-5) treated with diethylaluminum chloride had a maximum turnover frequency of 23,000 mole ethylene per mole Ni per hour, and a maximum selectivity for 1-butene of 80% under optimized conditions. Ethylene pressure strongly influenced the activity and selectivity of Ni-CPF-5. Though the observed activity behavior is similar, the selectivity trends diverged significantly from previously reported MOF dimerization catalysts.

Department dc:contributor.department

Massachusetts Institute of Technology. Department of Chemistry.

Grantor dc:publisher

Massachusetts Institute of Technology

Year dc:date.issued

2016

Author dc:creator

• Martin, Kathleen E. (Kathleen Ewing)

Advisor dc:contributor.advisor

• Mircea Dincă.

• Chemistry.

Statement dc:rights

• MIT theses are protected by copyright. They may be viewed, downloaded, or printed from this source but further reproduction or distribution in any format is prohibited without written permission.

Licence dc:rights.uri

• http://dspace.mit.edu/handle/1721.1/7582

Language dc:language.iso

eng

Handle dc:identifier.uri

http://hdl.handle.net/1721.1/107570

OAI identifier oai:identifier

oai:dspace.mit.edu:1721.1/107570