Esrafili Mehdi D, Khan Adnan Ali, Mousavian Parisasadat
Department of Chemistry, Faculty of Basic Sciences, University of Maragheh P. O. Box 55136-553 Maragheh Iran
Centre for Computational Materials Science, University of Malakand Chakdara Pakistan.
RSC Adv. 2021 Jun 28;11(37):22598-22610. doi: 10.1039/d1ra04046d. eCollection 2021 Jun 25.
The geometries, electronic structures, and catalytic properties of BN-codoped fullerenes C BN ( = 1-3) are studied using first-principles computations. The results showed that BN-codoping can significantly modify the properties of C 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 BN structures. The stepwise addition of N atoms around the B atom improves catalytic activities of C BN in NO reduction. The reduction of NO over CBN and CBN begins with its chemisorption on the B-C bond of the fullerene, followed by the concerted interaction of CO with NO and the release of N. The resulting OCO intermediate is subsequently transformed into a CO molecule, which is weakly adsorbed on the B atom of the fullerene. On the contrary, nitrogen-rich CBN fullerene is found to decompose NO into N 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 NO reduction on CBN fullerene is just 0.28 eV, which is lower than that of noble metals.
使用第一性原理计算方法研究了硼氮共掺杂富勒烯C₆₀BN（n = 1 - 3）的几何结构、电子结构和催化性能。结果表明，硼氮共掺杂能够通过打破局部电荷中性并产生活性位点来显著改变C₆₀富勒烯的性质。硼和氮的共掺杂提高了富勒烯的形成能，这表明这些原子的协同作用有助于稳定C₆₀BN结构。在硼原子周围逐步添加氮原子提高了C₆₀BN在NO还原反应中的催化活性。C₆₀BN和C₆₀BN上NO的还原反应始于其在富勒烯的B - C键上的化学吸附，随后CO与NO发生协同相互作用并释放出N。生成的OCO中间体随后转化为CO分子，该分子弱吸附在富勒烯的B原子上。相反，发现富氮的C₆₀BN富勒烯能够将NO分解为N和O物种，且无需活化能。然后CO分子以较低的活化能垒去除O物种。C₆₀BN富勒烯上NO还原反应的活化能垒仅为0.28 eV，低于贵金属的活化能垒。
