FeN_4掺杂对富勒烯催化特性调制的第一性原理研究  

First-principles study on the catalysis reactivity tuning of the fullerene from FeN_4 embedded

作　　者：薛洁[1] 王欢欢[1] 王裔喆 李硕[1] 路战胜[1] 杨宗献[1] 

机构地区：[1]河南师范大学物理与材料科学学院,新乡453007

出　　处：《原子与分子物理学报》2016年第6期1031-1035,共5页Journal of Atomic and Molecular Physics

基　　金：国家自然科学基金(11174070;11147006);河南省高校科技创新人才支持计划(15HASTIT016);河南省重点科技攻关项目(152102210083);大学生创新训练项目(201410476091)

摘　　要：因其较好的稳定性和催化活性,非金属N与金属共掺杂的富勒烯(C60)作为新型氧化还原反应(ORR)催化剂受到了人们的广泛关注.采用基于密度泛函理论的第一性原理方法系统地研究了Fe N4掺杂对C60催化特性的调制规律,揭示了O_2在Fe N4掺杂的C60上的吸附和氢化特性.结果表明:(1)O_2倾向于以side-on模式吸附在Fe的顶位上,O-O键平行于C60的球切面,与Fe形成O-Fe-O三元环结构,对应的吸附能为1.48 e V.(2)O_2的氢化反应路径可以分为两条:(i)O_2先解离为O+O,然后氢化为O+OH.O_2的解离为反应的速控步,势垒为2.82 e V.(ii)O_2先氢化形成OOH结构,然后解离.氢化为反应的速控步,势垒为2.83 e V.Given its good stability and activity,the nitrogen-doped and metal-coordinated Fullerene（C60） is attractive as a novel catalyst in oxygen reduction reaction（ORR）. Density functional theory including dispersion-corrected（DFT-D） is performed to investigate the mechanisms of tuning of the C60 from Fe N4 embedded,and theO_2 adsorption and hydrogenation on the Fe N4 embedded C60. It is found that：（1）O_2 prefers to stay on the top of Fe with the side-on configuration and oxygen-oxygen bonds are parallel to the surface of Fe N4 embedded C60,resulting in theO-Fe-O three member ring. The corresponding adsorption energy is 1. 48 e V.（2） Two kinds ofO_2 hydrogenation paths are presented：（i）O_2 decomposes intoO ＋O and then the atomicO is hydrogenated intoO ＋OH. The reaction rate-limiting step is the decomposition ofO_2 with the reaction barrier of 2. 82 e V.（ii）O_2 is firstly hydrogenated intoOOH and subsequently decomposes intoO ＋OH. The reaction rate-limiting step is hydrogenation ofO_2 with the reaction barrier of 2. 83 e V.

关 键 词：FeN4掺杂的C60 O2氢化 第一性原理研究 

分 类 号：O469[理学—凝聚态物理]