Transition metal(Fe, Ni, and Zn) doping-induced modulation of geometric and electronic structures to optimize the potential-determining step of MnCo2O4 for oxygen evolution reaction  

过渡金属诱导尖晶石氧化物几何与电子结构重组对氧析出反应的影响

作　　者：Lili Song Xiaoyun Zhang Shifan Zhu Yixue Xu Yuqiao Wang 宋利黎;张晓云;朱世璠;徐怡雪;王育乔(Research Center for Photoelectrochemistry and Devices,School of Chemistry and Chemical Engineering,Southeast University,Nanjing 211189,China)

机构地区：[1]Research Center for Photoelectrochemistry and Devices,School of Chemistry and Chemical Engineering,Southeast University,Nanjing 211189,China

出　　处：《Science China Materials》2022年第10期2871-2878,共8页中国科学（材料科学（英文版）

基　　金：financially supported by the National Natural Science Foundation of China (61774033)。

摘　　要：The electrocatalytic oxygen evolution reaction(OER)plays a critical role in the hydrogen energy industry[1–3].However,multiple electron transfer results in a sluggish kinetic process in the OER[4].The development of high-efficiency and low-cost OER catalysts is one of the keys to accelerating the kinetic process and widening practical OER applications.The spineltype transition-metal oxides(AB_(2)O_(4))have been used as OER electrocatalysts because of their potential activity and stability as the substitute of precious metals in the alkaline OER process[5].However,the electrochemical activity is limited by the less reactive sites and poor electrical conductivity owing to unsuitable geometric and electronic structures.催化剂的几何构型和电子结构对催化剂的性能有重大影响.在此我们以过渡金属铁、钴、锌分别掺杂尖晶石型氧化物MnCo_(2)O_(4)为理论模型,研究过渡金属原子掺杂对MnCo_(2)O_(4)几何构型和电子结构的调控机制及其对氧析出反应的作用机理.由于掺杂原子电负性的差异,通过掺杂会引起晶格收缩和电子结构重组.本文利用密度泛函理论计算预测:结构演变将激活晶格氧的反应性,不仅增强了尖晶石型氧化物的本征导电性,而且调控了该催化剂对中间体的吸附能力,实现了调节电压决定步骤和降低理论过电位的目的.通过理论筛选和实验发现:铁掺杂的MnCo_(2)O_(4)在氧析出反应中具有较低的过电位和良好的稳定性.

关 键 词：氧析出反应 密度泛函理论计算 几何构型 过渡金属 铁掺杂 过电位 调节电压 结构演变 

分 类 号：TQ426[化学工程] TQ116.2