Investigating the effect of metal nuclearity on activity for ethylene hydrogenation by metal-organic-framework-supported oxy-Ni(II) catalysts

Qining Wang, Zihan Pengmei, Riddhish Pandharkar, Laura Gagliardi, Joseph T. Hupp*, Justin M. Notestein

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

Abstract

Metal-organic frameworks (MOFs), thanks to their well-defined coordination sites, are promising for studying catalytically active structures. To understand the effect of metal nuclearity in MOF-supported catalysts, we adjusted the nuclearity of oxy-Ni(II) supported on the zirconia-like nodes of MOF NU-1000 by modulating the Ni loading, where the organic linkers served to prevent node-to-node migration of grafted nickel ions. At the single-node level, we grafted auxiliary structural linkers, naphthalene dicarboxylate, to reduce the number of binding/grafting sites. We found higher catalytic rates at higher Ni loading for ethylene hydrogenation on a per-nickel-ion basis, despite the similar chemical environment of Ni(II) at different loadings; catalysts consisting mainly of pairs of nickel ions were more reactive than those of single nickel ions. These observations illustrate the need for at least two proximal nickel ions for effective catalysis – presumably one for hydrogen binding and heterolytic splitting and one for ethylene binding and activation.

Original languageEnglish (US)
Pages (from-to)162-173
Number of pages12
JournalJournal of Catalysis
Volume407
DOIs
StatePublished - Mar 2022

Keywords

  • Active sites
  • Catalyst nuclearity
  • Ethylene hydrogenation
  • MOFs
  • Metal-organic frameworks
  • Nickel catalysts

ASJC Scopus subject areas

  • Catalysis
  • Physical and Theoretical Chemistry

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