Sulfur doped graphene as a promising metal-free electrocatalyst for oxygen reduction reaction: a DFT-D study
Sulfur doped graphene as a promising metal-free electrocatalyst for oxygen reduction reaction: a DFT-D study
复制标题
硫掺杂石墨烯作为一种有前途的氧还原反应无金属电催化剂：DFT-D 研究
DOI：
10.1039/c7ra00632b
复制
发表时间：
2017-04
期刊：
影响因子：
3.9
通讯作者：
Yang Zongxian
中科院分区：
文献类型：
--
作者：
Lu Zhansheng;Li Shuo;Liu Chuang;He Chaozheng;Yang Xinwei;Ma Dongwei;Xu Guoliang;Yang Zongxian
作为一种高效的无金属催化剂，掺杂杂原子的石墨烯在促进电化学氧还原反应（ORR）方面具有很高的活性。通过色散校正密度函数理论 (DFT-D) 计算研究了硫掺杂单空位石墨烯 (SGV) 上整个 ORR 过程的详细动力学和热力学行为以及原始机制。研究发现SGV相当稳定，硫掺杂剂可能是活性中心。根据动力学过程，提出了两种 ORR 途径：OOH 的解离和 OOH 的氢化，其速率决定步骤分别为 0.75 eV 和 0.62 eV。整个ORR的吉布斯自由能图表明OOH的解离被排除，因为O还原成OH的过程是吸热的，而HOOH的氢化即使在0.86 V的高电势下也是最有利的途径。我们的DFT-D模拟表明SGV将是ORR的有效电催化剂。
As an efficient metal-free catalyst, graphene doped with heteroatoms is highly active in promoting electrochemical oxygen reduction reaction (ORR). The detailed kinetic and thermodynamic behaviors of the entire ORR process on sulfur doped monovacancy graphene (SGV), as well as the original mechanism are investigated by the dispersion-corrected density function theory (DFT-D) calculations. It is found that the SGV is rather stable and the sulfur dopant is probably the active center. There are two proposed ORR pathways by kinetic process: the dissociation of OOH and the hydrogenation of OOH with the rate-determining steps of 0.75 eV and 0.62 eV, respectively. And the Gibbs free energy diagram of the entire ORR indicates that the dissociation of OOH is precluded, because the process of reduction step of O into OH is endothermic, while the hydrogenation of HOOH is the most favorable pathway even at high potential of 0.86 V. Our DFT-D simulation suggests that the SGV would be an efficient electrocatalyst for ORR.
登录
查看更多内容
影响因子：
6.6
作者：
J. Ozaki;S. Tanifuji;Atsuya Furuichi;Katsutoshi Yabutsuka
通讯作者：
J. Ozaki;S. Tanifuji;Atsuya Furuichi;Katsutoshi Yabutsuka
影响因子：
32.5
作者：
Jaouen, Frederic;Proietti, Eric;Zelenay, Piotr
通讯作者：
Zelenay, Piotr
影响因子：
7.3
作者：
Fazio, Gianluca;Ferrighi, Lara;Di Valentin, Cristiana
通讯作者：
Di Valentin, Cristiana
影响因子：
3.3
作者：
Norskov, JK;Rossmeisl, J;Jónsson, H
通讯作者：
Jónsson, H
影响因子：
64.8
作者：
Steele, BCH;Heinzel, A
通讯作者：
Heinzel, A