DFT Studies of Carbon Structures Supported Vanadia Catalysts for Oxidative Dehydrogenation of Propane: Kinetic and Thermodynamic

Year 2018, Volume: 46 Issue: 1, 79 - 89, 01.03.2018

Abdollah Fallah Shojaeı Ali-morad Rashıdı Mina Ghiasi Ghıası Robabe Mosavı

Abstract

The detailed mechanism for oxidative dehydrogenation of propane on the 1
VO4(CH3
)3 surface has been studied
in depth with density functional theory (DFT) calculations at the B3LYP level and standard split-valance basis
set, 6-31+G*. Monomeric vanadia specie was considered and modeled as catalysis. In addition, the mechanisms
of the two complete catalytic cycle, involving the regeneration of the reduced catalyst using O2 gaseous have
been reported. The reaction proceeds in two subsequent steps which at the first, one hydrogen abstracting
by the vanadium of V= O1 group with about 48.35 cal/mol activation energy is the rate determining step.
Subsequently, second intermediate has been formed through a bond formed between the propyl radical and O2
atom (V-O2). In continue, the O1 atom abstracts one hydrogen atom from the methyl group with a 131.63 kcal/
mol barrier to form propene by passing to second transition state. The results of our calculations have found
that all the reactions involve vanadyl oxygen (V=O1), with the bridging oxygen (V-O-C) serving to stabilize the
isopropyl radical intermediate.

Keywords

Vanadia, propane, oxidative dehydrogenation, DFT calculation

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