Metal-organic framework supported single-site nickel catalysts for butene dimerization

Jian Zheng, Laura Löbbert, Saumil Chheda, Navneet Khetrapal, Julian Schmid, Carlo Alberto Gaggioli, Benjamin Yeh, Ricardo Bermejo-Deval, Radha Kishan Motkuri, Mahalingam Balasubramanian, John L. Fulton, Oliver Y. Gutiérrez, J. Ilja Siepmann, Matthew Neurock, Laura Gagliardi, Johannes A. Lercher

Research output: Contribution to journalArticlepeer-review

9 Scopus citations


Homotopic sites in a well-controlled environment are not only ideal systems for mechanistic studies, but also allow optimal control of catalytic transformations. Sites having only a single metal cation and sites consisting of metal oxo complexes with few nickel (Ni) cations supported on the nodes of UiO-66 metal–organic framework (Ni-UiO-66) are studied for 1-butene dimerization. Monomeric Ni sites, which bind to the Zr6 node via two Zr-OH(μ3) linkages, are active and selective for the dimerization of 1-butene to linear and mono-branched C8 isomers. Ni oxo complexes with few Ni cations show lower activity and promote the oligomerization of transiently formed C8 isomers. Kohn-Sham density function theory calculations combined with spectroscopic measurements and kinetic analyses indicate that dimerization follows a Cossee-Arlman reaction mechanism.

Original languageEnglish (US)
Pages (from-to)176-183
Number of pages8
JournalJournal of Catalysis
StatePublished - Sep 2022

Bibliographical note

Funding Information:
The authors gratefully acknowledge support for this work from the Inorganometallic Catalyst Design Center, which is an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences (DE-SC0012702). Most of the experiments were performed at Pacific Northwest National Laboratory (PNNL), which is operated by Battelle for DOE. This research used resources of the Advanced Photon Source (APS), which is a DOE Office of Science, Office of Basic Energy Sciences scientific user facility. Sector 20 operations at the APS are supported by DOE (DE-AC02-06CH11357) and the Canadian Light Source. Part of this work was also performed at Stanford Synchrotron Radiation Lightsource (SSRL) of SLAC National Accelerator Laboratory by Co-ACCESS, supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division. DFT calculations were performed at the Minnesota Supercomputing Institute at the University of Minnesota. The authors would also like to thank Professor Aditya Bhan and Professor Connie Liu at the University of Minnesota for helpful discussions and Roshan Patel for carrying out Monte Carlo simulations.

Publisher Copyright:
© 2022


  • Alkene dimerization
  • Heterogeneous catalysis
  • Metal–organic framework
  • Reaction mechanism
  • Single site catalyst


Dive into the research topics of 'Metal-organic framework supported single-site nickel catalysts for butene dimerization'. Together they form a unique fingerprint.

Cite this