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 N 2 O gas.

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 C 60 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 N 2 O reduction. The reduction of N 2 O over C 58 BN and C 57 BN 2 begins with its chemisorption on the B-C bond of the fullerene, followed by the concerted interaction of CO with N 2 O and the release of N 2 . The resulting OCO intermediate is subsequently transformed into a CO 2 molecule, which is weakly adsorbed on the B atom of the fullerene. On the contrary, nitrogen-rich C 56 BN 3 fullerene is found to decompose N 2 O into N 2 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 N 2 O reduction on C 56 BN 3 fullerene is just 0.28 eV, which is lower than that of noble metals.