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Title: Understanding oxidative dehydrogenation of ethane on Co 3O 4 nanorods from density functional theory

Co 3O 4 is a metal oxide catalyst with weak, tunable M–O bonds promising for catalysis. Here, density functional theory (DFT) is used to study the oxidative dehydrogenation (ODH) of ethane on Co 3O 4 nanorods based on the preferred surface orientation (111) from the experimental electron-microscopy image. The pathway and energetics of the full catalytic cycle including the first and second C–H bond cleavages, hydroxyl clustering, water formation, and oxygen-site regeneration are determined. We find that both lattice O and Co may participate as active sites in the dehydrogenation, with the lattice-O pathway being favored. Here, we identify the best ethane ODH pathway based on the overall energy profiles of several routes. We identify that water formation from the lattice oxygen has the highest energy barrier and is likely a rate-determining step. This work of the complete catalytic cycle of ethane ODH will allow further study into tuning the surface chemistry of Co 3O 4 nanorods for high selectivity of alkane ODH reactions.
Authors:
 [1] ;  [2] ;  [1]
  1. Univ. of California, Riverside, CA (United States). Dept. of Chemistry
  2. (Feng) [Univ. of Kansas, Lawrence, KS (United States). Dept. of Chemical and Petroleum Engineering and Dept. of Chemistry
Publication Date:
Grant/Contract Number:
SC0014561
Type:
Accepted Manuscript
Journal Name:
Catalysis Science and Technology
Additional Journal Information:
Journal Volume: 6; Journal Issue: 18; Journal ID: ISSN 2044-4753
Publisher:
Royal Society of Chemistry
Research Org:
Univ. of California, Riverside, CA (United States). Dept. of Chemistry
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1437014

Fung, Victor, Tao, Franklin, and Jiang, De-en. Understanding oxidative dehydrogenation of ethane on Co3O4 nanorods from density functional theory. United States: N. p., Web. doi:10.1039/c6cy00749j.
Fung, Victor, Tao, Franklin, & Jiang, De-en. Understanding oxidative dehydrogenation of ethane on Co3O4 nanorods from density functional theory. United States. doi:10.1039/c6cy00749j.
Fung, Victor, Tao, Franklin, and Jiang, De-en. 2016. "Understanding oxidative dehydrogenation of ethane on Co3O4 nanorods from density functional theory". United States. doi:10.1039/c6cy00749j. https://www.osti.gov/servlets/purl/1437014.
@article{osti_1437014,
title = {Understanding oxidative dehydrogenation of ethane on Co3O4 nanorods from density functional theory},
author = {Fung, Victor and Tao, Franklin and Jiang, De-en},
abstractNote = {Co3O4 is a metal oxide catalyst with weak, tunable M–O bonds promising for catalysis. Here, density functional theory (DFT) is used to study the oxidative dehydrogenation (ODH) of ethane on Co3O4 nanorods based on the preferred surface orientation (111) from the experimental electron-microscopy image. The pathway and energetics of the full catalytic cycle including the first and second C–H bond cleavages, hydroxyl clustering, water formation, and oxygen-site regeneration are determined. We find that both lattice O and Co may participate as active sites in the dehydrogenation, with the lattice-O pathway being favored. Here, we identify the best ethane ODH pathway based on the overall energy profiles of several routes. We identify that water formation from the lattice oxygen has the highest energy barrier and is likely a rate-determining step. This work of the complete catalytic cycle of ethane ODH will allow further study into tuning the surface chemistry of Co3O4 nanorods for high selectivity of alkane ODH reactions.},
doi = {10.1039/c6cy00749j},
journal = {Catalysis Science and Technology},
number = 18,
volume = 6,
place = {United States},
year = {2016},
month = {5}
}

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