DFT investigation of hydroperoxide decomposition over copper and cobalt sites within metal-organic frameworks

Patrick Ryan, Ivan Konstantinov, Randall Q. Snurr*, Linda J. Broadbelt

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

19 Scopus citations

Abstract

Experimental results in the literature show that two metal-organic frameworks (MOFs) containing copper and cobalt nodes are active for hydroperoxide decomposition, which is an important reaction in auto-oxidation processes. Density functional theory (DFT) calculations reported here for these systems suggest that the metal sites in the interior of these MOFs are not the active sites for this type of reaction due to the steric effects of the adjacent linkers. This implies that the experimental catalysis observed may occur on the exterior surface of the MOF crystals. Additional calculations with a copper paddlewheel node show that, despite being able to form complexes with hydroperoxides, the metal sites in copper paddlewheels do not catalyze hydroperoxide decomposition. Preliminary calculations involving undercoordinated metal atoms as a model for metal sites on the MOF exterior crystal surface suggest that these sites could be catalytically active.

Original languageEnglish (US)
Pages (from-to)95-102
Number of pages8
JournalJournal of Catalysis
Volume286
DOIs
StatePublished - Feb 2012

Keywords

  • Catalysis
  • DFT
  • Haber-Weiss cycle
  • Metal-organic framework
  • Peroxide decomposition

ASJC Scopus subject areas

  • Catalysis
  • Physical and Theoretical Chemistry

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