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C 59 N Heterofullerene: A Promising Catalyst for NO Conversion into N 2 O
Author(s) -
Esrafili Mehdi D.,
Heidari Safa
Publication year - 2019
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.201900277
Subject(s) - molecule , dissociation (chemistry) , catalysis , fullerene , density functional theory , chemistry , dopant , moiety , atom (system on chip) , doping , crystallography , computational chemistry , materials science , stereochemistry , organic chemistry , optoelectronics , computer science , embedded system
We report, for the first time, the possibility of using N‐doped C 60 fullerene (C 59 N) as a novel and highly active metal‐free catalyst for reduction of NO molecules to N 2 O. First‐principles density functional theory calculations are used to find the most energetically favorable adsorbed/coadsorbed configurations of NO molecules over C 59 N. Our results indicate that introducing a N impurity in C 60 can induce a positive charge and large spin density over the carbon atoms nearest to the dopant atom. Consequently, these carbon atoms are identified as the most reactive sites to interact with the NO molecule. According to our results, the dissociation of NO molecule over C 59 N is almost impossible, due to its relatively high activation energy (1.35 eV). The reduction of NO over C 59 N starts with the coadsorption of two NO molecules to form (NO) 2 species, followed by the dissociation of (NO) 2 into N 2 O and an active atomic oxygen (O ads ). The energy barrier to convert NO molecules into N 2 O ranges from 0.33 to 0.75 eV, which indicates this process is likely to proceed at normal temperature. Besides, by overcoming a negligible energy barrier (0.18 eV), the remaining O ads moiety can be easily eliminated by a CO molecule. To further understand the role of nitrogen atoms in the NO reduction process, the catalytic performance of high percentage N‐doped fullerene (C 48 N 12 ) is also studied.