Zhang Xiaoming, Xia Zhangxun, Li Huanqiao, Yu Shansheng, Wang Suli, Sun Gongquan
Division of Fuel Cells and Battery, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences Dalian 116023 China
Department of Materials Science, Jilin University Changchun 130012 China.
RSC Adv. 2019 Mar 1;9(13):7086-7093. doi: 10.1039/c9ra00167k.
Heteroatom doped graphene as a single-atom catalyst for oxygen reduction reaction (ORR) has received extensive attention in recent years. In this paper, the ORR activity of defective graphene anchoring single heteroatom (IIIA, IVA, VA, VIA and VIIA) was systematically investigated using a dispersion-corrected density functional theory method. For all of the 34 catalysts, 14 of which were further analyzed, and the Gibbs free energy of each elementary reaction was calculated. According to the scaling relationship between Δ and Δ , we further analyzed the rate-determining step of the remaining 20 catalysts. The results show that when the ORR reaction proceeds in the path O → OOH → O → OH → HO, the reaction energy barriers are lower than 0.8 eV for Te-SV, Sb-DV, Pb-SV, Pb-DV, As-SV, As-DV, B-SV, Sn-SV and N-SV. Our result provides a theoretical basis for further exploration of carbon-based single-atom catalysts for ORR.
近年来，杂原子掺杂的石墨烯作为氧还原反应（ORR）的单原子催化剂受到了广泛关注。本文采用色散校正密度泛函理论方法，系统研究了缺陷石墨烯锚定单杂原子（IIIA、IVA、VA、VIA和VIIA）的ORR活性。对所有34种催化剂中的14种进行了进一步分析，并计算了每个基元反应的吉布斯自由能。根据Δ与Δ之间的标度关系，进一步分析了其余20种催化剂的速率决定步骤。结果表明，当ORR反应按O→OOH→O→OH→HO路径进行时，Te-SV、Sb-DV、Pb-SV、Pb-DV、As-SV、As-DV、B-SV、Sn-SV和N-SV的反应能垒低于0.8 eV。我们的结果为进一步探索用于ORR的碳基单原子催化剂提供了理论依据。
