Theoretical insights into direct methane to methanol conversion over supported dicopper oxo nanoclusters

Hieu A. Doan, Zhanyong Li, Omar K. Farha, Joseph T. Hupp, Randall Q. Snurr

Research output: Contribution to journalArticle

8 Citations (Scopus)


The prospect of using copper oxide nanoclusters grown by atomic layer deposition on a porphyrin support for selective oxidation of methane to methanol was examined by means of density functional theory (DFT) calculations. Ab initio thermodynamic analysis indicates that an active site in the form of Cu(μ-O)Cu can be stabilized by activation in O2 at 465 K. Furthermore, a moderate methane activation energy barrier (Ea = 54 kJ/mol) is predicted, and the hydrogen abstraction activity of the active site could be attributed to the radical character of the bridging oxygen. Methanol extraction in this system is limited by a thermodynamic barrier to desorption of ΔG = 57 kJ/mol at 473 K; however, desorption can be facilitated by the addition of water in a “stepped conversion” process. Overall, our results indicate similar activity between porphyrin-supported copper oxide nanoclusters and existing Cu-exchanged zeolites and provide a computational proof-of-concept for utilizing functionalized organic linkers in metal-organic frameworks (MOFs) for selective oxidation of methane to methanol.

Original languageEnglish
Pages (from-to)2-9
Number of pages8
JournalCatalysis Today
Publication statusPublished - Aug 15 2018


  • Atomic layer deposition
  • C1 chemistry
  • Copper
  • DFT
  • Methane to methanol
  • Porphyrin

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

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