Structure and activity of mixed VOx-CeO2 domains supported on alumina in cyclohexane oxidative dehydrogenation

Izabela A. Samek, N. Scott Bobbitt, Randall Q. Snurr*, Peter C. Stair

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

20 Scopus citations

Abstract

Alumina-supported VOx-CeO2 materials are synthesized by atomic layer deposition (ALD) and evaluated in cyclohexane oxidative dehydrogenation (ODH). The order of deposition of the two metal oxides by ALD influences the size, geometry and oxidation state of the resulting surface species as indicated by Raman spectroscopy coupled with density functional theory (DFT) calculations and XPS. The individual contributions of VOx and CeO2 surface sites to the cyclohexane ODH reaction mechanism are investigated through a comparison of the catalytic activity of the supported mixed metal oxide materials, VOx/Al2O3, VOx/CeO2 and a bare CeO2 support. The highest activity is observed for CeO2, and different surface active sites are distinguished by introducing cyclohexane and cyclohexene in the reactant feed mixture. The catalytic behavior is dependent on the nature of V–O–S (S, Support) bonds, and small clusters of CeO2 on Al2O3 favor total oxidation, similar to exposed CeO2 sites in VOx/CeO2.

Original languageEnglish (US)
Pages (from-to)147-158
Number of pages12
JournalJournal of Catalysis
Volume384
DOIs
StatePublished - Apr 2020

Funding

This material is based upon work supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DOE DE-FG02-03-ER154757. The REACT Facility of the Northwestern University Center for Catalysis and Surface Science is supported by a grant from the DOE (DE-SC0001329). This work made use of the Keck-II facility of Northwestern University’s NUANCE Center, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205); the MRSEC program (NSF DMR-1720139) at the Materials Research Center; the International Institute for Nanotechnology (IIN); the Keck Foundation; and the State of Illinois, through the IIN. Metal analysis was performed at the Northwestern University Quantitative Bioelement Imaging Center. I.A.S. would like to thank Rebecca Sponenburg for performing the metal analysis. This research was supported in part through the computational resources and staff contributions provided for the Quest high performance computing facility at Northwestern University which is jointly supported by the Office of the Provost, the Office for Research, and Northwestern University Information Technology. This research used resources of the National Energy Research Scientific Computing Center (NERSC), a U.S. Department of Energy Office of Science User Facility operated under Contract No. DE-AC02-05CH11231.

Keywords

  • Atomic layer deposition
  • Cerium oxide
  • Cyclohexane
  • DFT
  • Oxidative dehydrogenation
  • Supported vanadium oxide

ASJC Scopus subject areas

  • Catalysis
  • Physical and Theoretical Chemistry

Fingerprint

Dive into the research topics of 'Structure and activity of mixed VOx-CeO2 domains supported on alumina in cyclohexane oxidative dehydrogenation'. Together they form a unique fingerprint.

Cite this