The Molecular Path Approaching the Active Site in Catalytic Metal-Organic Frameworks

Ana E. Platero-Prats, Andreas Mavrandonakis, Jian Liu, Zhihengyu Chen, Zhijie Chen, Zhanyong Li, Andrey A. Yakovenko, Leighanne C. Gallington, Joseph T. Hupp, Omar K. Farha, Christopher J. Cramer, Karena W. Chapman*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

14 Scopus citations


How molecules approach, bind at, and release from catalytic sites is key to heterogeneous catalysis, including for emerging metal-organic framework (MOF)-based catalysts. We use in situ synchrotron X-ray scattering analysis to evaluate the dominant binding sites for reagent and product molecules in the vicinity of catalytic Ni-oxo clusters in NU-1000 with different surface functionalization under conditions approaching those used in catalysis. The locations of the reagent and product molecules within the pores can be linked to the activity for ethylene hydrogenation. For the most active catalyst, ethylene reagent molecules bind close to the catalytic clusters, but only at temperatures approaching experimentally observed onset of catalysis. The ethane product molecules favor a different binding location suggesting that the product is readily released from the active site. An unusual guest-dependence of the framework negative thermal expansion is documented. We hypothesize that reagent and product binding sites reflect the pathway through the MOF to the active site and can be used to identify key factors that impact the catalytic activity.

Original languageEnglish (US)
Pages (from-to)20090-20094
Number of pages5
JournalJournal of the American Chemical Society
Issue number48
StatePublished - Dec 8 2021

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry


Dive into the research topics of 'The Molecular Path Approaching the Active Site in Catalytic Metal-Organic Frameworks'. Together they form a unique fingerprint.

Cite this