Synergic effects between boron and nitrogen atoms in BN-codoped C59- n BN n fullerenes (n = 1-3) for metal-free reduction of greenhouse N2O gas

Mehdi D Esrafili; Adnan Ali Khan; Parisasadat Mousavian

doi:10.1039/d1ra04046d

Synergic effects between boron and nitrogen atoms in BN-codoped C_{59- n} BN _n fullerenes (n = 1-3) for metal-free reduction of greenhouse N₂O gas

RSC Adv. 2021 Jun 28;11(37):22598-22610. doi: 10.1039/d1ra04046d. eCollection 2021 Jun 25.

Authors

Mehdi D Esrafili¹, Adnan Ali Khan^{2

3}, Parisasadat Mousavian^{1

4}

Affiliations

¹ Department of Chemistry, Faculty of Basic Sciences, University of Maragheh P. O. Box 55136-553 Maragheh Iran esrafili@maragheh.ac.ir.
² Centre for Computational Materials Science, University of Malakand Chakdara Pakistan.
³ Department of Chemistry, University of Malakand Chakdara Pakistan.
⁴ Department of Chemistry, Azarbaijan Shahid Madani University Tabriz Iran.

Abstract

The geometries, electronic structures, and catalytic properties of BN-codoped fullerenes C_59-n BN _n (n = 1-3) are studied using first-principles computations. The results showed that BN-codoping can significantly modify the properties of C₆₀ fullerene by breaking local charge neutrality and creating active sites. The codoping of B and N enhances the formation energy of fullerenes, indicating that the synergistic effects of these atoms helps to stabilize the C_59-n BN _n structures. The stepwise addition of N atoms around the B atom improves catalytic activities of C_59-n BN _n in N₂O reduction. The reduction of N₂O over C₅₈BN and C₅₇BN₂ begins with its chemisorption on the B-C bond of the fullerene, followed by the concerted interaction of CO with N₂O and the release of N₂. The resulting OCO intermediate is subsequently transformed into a CO₂ molecule, which is weakly adsorbed on the B atom of the fullerene. On the contrary, nitrogen-rich C₅₆BN₃ fullerene is found to decompose N₂O into N₂ and O* species without the requirement for activation energy. The CO molecule then removes the O* species with a low activation barrier. The activation barrier of the N₂O reduction on C₅₆BN₃ fullerene is just 0.28 eV, which is lower than that of noble metals.