Why Boron Nitride is such a Selective Catalyst for the Oxidative Dehydrogenation of Propane
Abstract
Boron–containing materials, and in particular boron nitride, have recently been identified as highly selective catalysts for the oxidative dehydrogenation of alkanes such as propane. To date, no mechanism exists that can explain both the unprecedented selectivity, the observed surface oxyfunctionalization, and the peculiar kinetic features of this reaction. Here, we combine catalytic activity measurements with quantum chemical calculations to put forward a bold new hypothesis. We argue that the remarkable product distribution can be rationalized by a combination of surface–mediated formation of radicals over metastable sites, and their sequential propagation in the gas phase. Based on known radical propagation steps, we quantitatively describe the oxygen pressure–dependent relative formation of the main product propylene and by–product ethylene. Free radical intermediates most likely differentiate this catalytic system from less selective vanadium–based catalysts.
- Authors:
-
[1];
[2];
[3];
[3];
[2];
[3]
- Univ. of Wisconsin, Madison, WI (United States); The Dow Chemical Company, Midland, MI (United States)
- Univ. of California, Los Angeles, CA (United States)
- Univ. of Wisconsin, Madison, WI (United States)
- Publication Date:
- Research Org.:
- Univ. of Wisconsin, Madison, WI (United States); Univ. of California, Los Angeles, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division
- OSTI Identifier:
- 1866356
- Alternate Identifier(s):
- OSTI ID: 1638395; OSTI ID: 1755413
- Grant/Contract Number:
- SC0017918; SC0019152; AC02-05CH11231; AC02‐05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Angewandte Chemie (International Edition)
- Additional Journal Information:
- Journal Name: Angewandte Chemie (International Edition); Journal Volume: 59; Journal Issue: 38; Journal ID: ISSN 1433-7851
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 03 NATURAL GAS; 36 MATERIALS SCIENCE; 42 ENGINEERING; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Boron nitride; boron oxide; radical chemistry; surface oxidation; water promotion
Citation Formats
Venegas, Juan M., Zhang, Zisheng, Agbi, Theodore O., McDermott, William P., Alexandrova, Anastassia, and Hermans, Ive. Why Boron Nitride is such a Selective Catalyst for the Oxidative Dehydrogenation of Propane. United States: N. p., 2020.
Web. doi:10.1002/anie.202003695.
Venegas, Juan M., Zhang, Zisheng, Agbi, Theodore O., McDermott, William P., Alexandrova, Anastassia, & Hermans, Ive. Why Boron Nitride is such a Selective Catalyst for the Oxidative Dehydrogenation of Propane. United States. https://doi.org/10.1002/anie.202003695
Venegas, Juan M., Zhang, Zisheng, Agbi, Theodore O., McDermott, William P., Alexandrova, Anastassia, and Hermans, Ive. Mon .
"Why Boron Nitride is such a Selective Catalyst for the Oxidative Dehydrogenation of Propane". United States. https://doi.org/10.1002/anie.202003695. https://www.osti.gov/servlets/purl/1866356.
@article{osti_1866356,
title = {Why Boron Nitride is such a Selective Catalyst for the Oxidative Dehydrogenation of Propane},
author = {Venegas, Juan M. and Zhang, Zisheng and Agbi, Theodore O. and McDermott, William P. and Alexandrova, Anastassia and Hermans, Ive},
abstractNote = {Boron–containing materials, and in particular boron nitride, have recently been identified as highly selective catalysts for the oxidative dehydrogenation of alkanes such as propane. To date, no mechanism exists that can explain both the unprecedented selectivity, the observed surface oxyfunctionalization, and the peculiar kinetic features of this reaction. Here, we combine catalytic activity measurements with quantum chemical calculations to put forward a bold new hypothesis. We argue that the remarkable product distribution can be rationalized by a combination of surface–mediated formation of radicals over metastable sites, and their sequential propagation in the gas phase. Based on known radical propagation steps, we quantitatively describe the oxygen pressure–dependent relative formation of the main product propylene and by–product ethylene. Free radical intermediates most likely differentiate this catalytic system from less selective vanadium–based catalysts.},
doi = {10.1002/anie.202003695},
journal = {Angewandte Chemie (International Edition)},
number = 38,
volume = 59,
place = {United States},
year = {Mon Jun 22 00:00:00 EDT 2020},
month = {Mon Jun 22 00:00:00 EDT 2020}
}
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