The geometries, electronic structures, and catalytic properties of BN-codoped fullerenes C59-nBNn (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 C59-nBNn structures. The stepwise addition of N atoms around the B atom improves catalytic activities of C59-nBNn 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.
