Premium
Why Boron Nitride is such a Selective Catalyst for the Oxidative Dehydrogenation of Propane
Author(s) -
Venegas Juan M.,
Zhang Zisheng,
Agbi Theodore O.,
McDermott William P.,
Alexandrova Anastassia,
Hermans Ive
Publication year - 2020
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202003695
Subject(s) - dehydrogenation , propane , catalysis , boron nitride , chemistry , photochemistry , selectivity , boron , product distribution , radical , ethylene , metastability , inorganic chemistry , organic chemistry
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. 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.