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Title: The mechanism and kinetics of propene ammoxidation over α-bismuth molybdate

Propene ammoxidation over Bi 2Mo 3O 12 was investigated to elucidate product (acrylonitrile, acetonitrile, HCN, acrolein, N 2, etc.) formation pathways. Propene consumption rate is first order in propene and zero order in ammonia (for NH 3/C 3H 6 = 0-2) and oxygen (for O 2 /C 3 H 6 ≥ 1.5) partial pressures, with an activation energy (E a = 22 kcal/mol) comparable to that for propene oxidation, suggesting the same rate-limiting step for both reactions. We propose two N-containing species are relevant at ammoxidation conditions: adsorbed NH 3 on surface Bi 3+ ions that reacts with a propene derivative to form products with C-N bonds, and a few metastable M-NH x (M = Mo, Bi; x = 1, 2) groups that are very sensitive to destruction by water, but that are responsible for NH 3 oxidation to N 2. A proposed reaction mechanism and model that captures the experimental trends in product distribution as a function of partial pressures and temperature are presented.
Authors:
 [1] ;  [1] ;  [1]
  1. Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering
Publication Date:
Grant/Contract Number:
AC02-05CH11231; CHE-0840505
Type:
Accepted Manuscript
Journal Name:
Journal of Catalysis
Additional Journal Information:
Journal Volume: 339; Journal ID: ISSN 0021-9517
Publisher:
Elsevier
Research Org:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org:
SC-22.1 USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; USDOE
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Bismuth molybdate; Selective ammoxidation; Propene; Ammonia; Acrylonitrile
OSTI Identifier:
1418290
Alternate Identifier(s):
OSTI ID: 1341150

Licht, Rachel B., Vogt, Diana, and Bell, Alexis T.. The mechanism and kinetics of propene ammoxidation over α-bismuth molybdate. United States: N. p., Web. doi:10.1016/j.jcat.2016.04.012.
Licht, Rachel B., Vogt, Diana, & Bell, Alexis T.. The mechanism and kinetics of propene ammoxidation over α-bismuth molybdate. United States. doi:10.1016/j.jcat.2016.04.012.
Licht, Rachel B., Vogt, Diana, and Bell, Alexis T.. 2016. "The mechanism and kinetics of propene ammoxidation over α-bismuth molybdate". United States. doi:10.1016/j.jcat.2016.04.012. https://www.osti.gov/servlets/purl/1418290.
@article{osti_1418290,
title = {The mechanism and kinetics of propene ammoxidation over α-bismuth molybdate},
author = {Licht, Rachel B. and Vogt, Diana and Bell, Alexis T.},
abstractNote = {Propene ammoxidation over Bi2Mo3O12 was investigated to elucidate product (acrylonitrile, acetonitrile, HCN, acrolein, N2, etc.) formation pathways. Propene consumption rate is first order in propene and zero order in ammonia (for NH3/C3H6 = 0-2) and oxygen (for O2 /C3 H6 ≥ 1.5) partial pressures, with an activation energy (Ea = 22 kcal/mol) comparable to that for propene oxidation, suggesting the same rate-limiting step for both reactions. We propose two N-containing species are relevant at ammoxidation conditions: adsorbed NH3 on surface Bi3+ ions that reacts with a propene derivative to form products with C-N bonds, and a few metastable M-NHx (M = Mo, Bi; x = 1, 2) groups that are very sensitive to destruction by water, but that are responsible for NH3 oxidation to N2. A proposed reaction mechanism and model that captures the experimental trends in product distribution as a function of partial pressures and temperature are presented.},
doi = {10.1016/j.jcat.2016.04.012},
journal = {Journal of Catalysis},
number = ,
volume = 339,
place = {United States},
year = {2016},
month = {5}
}