MN_(x)O_(4-x)作为ORR/OER活性位点的电催化性能研究  

Electrocatalytic Performance of MN_(x)O_(4-x)as Active Sites for ORR/OER

作　　者：卫诗倩 刘馨蕊 赵云舒 陈茂霞 吕申壮 范强[1,2] 王芳 胡育[1,2] Wei Shiqian;Liu Xinrui;Zhao Yunshu;Chen Maoxia;Lv Shenzhuang;Fan Qiang;Wang Fang;Hu Yu(School of New Energy Materials and Chemistry,Leshan Normal University,Leshan 614004,China;Leshan West Silicon Materials Photovoltaic and New Energy Industry Technology Research Institute,Leshan 614000,China;School of New Energy and Materials,Southwest Petroleum University,Chengdu 610500,China)

机构地区：[1]乐山师范学院新能源材料与化学学院,四川乐山614004 [2]乐山西部硅材料光伏新能源光伏产业技术研究院,四川乐山614000 [3]西南石油大学新能源与材料学院,四川成都610500

出　　处：《稀有金属材料与工程》2024年第8期2250-2258,共9页Rare Metal Materials and Engineering

基　　金：乐山师范学院博士人才启动项目(RC202007);晶硅光伏新能源研究院开放课题(2022CHXK005);乐山师范学院校级学科建设重点科研项目(LZD024);天然产物化学与小分子催化四川省高校重点实验室开放基金(TRCWYXFZCH2022B05);乐山市重点科技计划(21GZD002);大学生创新创业训练计划(S202210649101)。

摘　　要：目前开发双功能电催化剂是解决金属-空气电池和燃料电池氧电极电化学过程缓慢及能量转化效率低等问题的重要手段之一,其中负载过渡金属单原子的氮掺杂石墨烯材料(M-N-C)被认为是最有希望替代贵金属的催化材料。研究表明M-N-C催化剂的高活性归因于其中过渡金属-氮氧配合物(MN_(x)O_(4-x))的存在,为了探究MN_(x)O_(4-x)配位结构对材料催化性能的影响,本研究基于第一性原理,通过在Fe-N-C材料中引入氧构建不同的FeN_(x)O_(4-x)(x=0,1,2,3,4)配合物,研究金属原子的配位数x对氧还原反应(ORR)和氧析出反应(OER)催化性能的影响。结果表明,具有FeN_(4)配位结构的Fe-N-C材料热力学稳定性及ORR/OER催化性能最佳。此外,本研究通过变换过渡金属的种类,即锰、铁、钴、镍、铜(M=Mn、Fe、Co、Ni、Cu),研究过渡金属的种类M对MN4催化活性的影响。研究发现,具有CoN_(4)配位结构的M-N-C材料热力学稳定,且相较于其他MN4其ORR和OER催化性能最佳。本研究结果可为调节过渡金属单原子的配位环境,设计高效双功能电催化剂提供理论参考。At present,developing bifunctional electrocatalysts plays an important role in the field of metal-air batteries and fuel cells.Non-noble transition metal single atoms loaded on the nitrogen-doped graphene sheets(M-N-C)are considered to be the most promising materials to replace noble metal electrocatalysts owing to the metal coordination compounds(MN_(x)O_(4-x))in M-N-C with high catalytic activity.In this work,oxygen atoms were introduced in Fe-N-C to construct FeN_(x)O_(4-x)(x=0,1,2,3,4)for the investigation on the effect of coordination number x on the catalytic performance of ORR/OER.It is found that Fe-N-C shows the best thermodynamic stability and catalytic activity when x=4.In addition,the effect of transition metal type was studied by introducing different transition metals,such as M=Mn,Fe,Co,Ni,Cu,in MN_(4).Among them,the thermodynamically stable CoN_(4)structure is the best choice for M-N-C to reach the highest ORR/OER catalytic activity.It is expected that this research could provide a theoretical reference for adjusting the coordination environment of transition metal single atoms and designing high efficient bifunctional electrocatalysts.

关 键 词：氮掺杂石墨烯 过渡金属单原子 氧还原反应 析氧反应 第一性原理 

分 类 号：O643.36[理学—物理化学]