1Department of Nanoporous and Nanosized Carbon Materials, O. Chuiko Institute of Surface Chemistry, NAS of Ukraine, 17 General Naumov Street, Kyiv 03164 Ukraine
2China-Central and Eastern Europe International Science and Technology Achievement Transfer Center, Ningbo University of Technology, 201 Fenghua Road, Ningbo 315211, China
3Department of Photonic Crystals, V. Lashkaryov Institute of Semiconductor Physics, NAS of Ukraine, 41 Prospect Nauki, Kyiv 03028, Ukraine
Adv. Mater. Lett., 2018, 9 (6), pp 450-455
Publication Date (Web): May 17, 2018
Copyright © IAAM-VBRI Press
The possible mechanisms of decomposition of benzoyl peroxide were investigated by the method of density functional theory with the exchange-correlation functionality of B3LYP, a basis set of 6-31G (d, p). It was carried out a comparative analysis of the quantum chemical calculations of the electronic structure of carbon nanoclusters simulating the active surface of sp2 carbon materials, including their modifications by the heteroatoms N and O. The energy parameters of the benzoyl peroxide molecule and all possible products of its decomposition, as well as the interaction of the free radical Ph-COO• with model graphite-like nanoclusters were considered. The calculations are compared with the experimental results of the catalytic activity of the varieties of activated charcoal and the catalase enzyme in the reaction of the benzoyl peroxide decomposition in a non-aqueous medium. It has been established that in the benzoyl peroxide molecule, regardless of the polarity of the medium, the weakest is the bond (O-O). The greatest ability to decompose benzoyl peroxide, which is much larger than that of catalase, was detected on the N-containing carbonaceous materials. It is shown that the free radical Ph-COO• is lighter and kinetically, and thermodynamically interacted with the graphite-like plane of the model N-containing carbon nanoclusters.
Carbon materials, benzoyl peroxide, catalytic activity, reaction mechanism, quantum chemistry, density function theory method, cluster approximation.