文献类型：期刊文献

英文题名：First-principles study of the oxygen reduction reaction on the boron-doped C9N4 metal-free catalyst

作者：He, Bingling[1,2,3];Shen, Jiansheng[1];Lu, Zhansheng[4];Ma, Dongwei[2,3]

第一作者：He, Bingling;赫丙玲

通讯作者：Ma, DW[1];Ma, DW[2]

机构：[1]Xinxiang Univ, Coll Phys & Elect Engn, Xinxiang 453003, Henan, Peoples R China;[2]Henan Univ, Key Lab Special Funct Mat, Minist Educ, Kaifeng 475004, Peoples R China;[3]Henan Univ, Sch Mat Sci & Engn, Kaifeng 475004, Peoples R China;[4]Henan Normal Univ, Coll Phys, Xinxiang 453007, Henan, Peoples R China

第一机构：新乡学院物理与电子工程学院

通讯机构：[1]corresponding author), Henan Univ, Key Lab Special Funct Mat, Minist Educ, Kaifeng 475004, Peoples R China;[2]corresponding author), Henan Univ, Sch Mat Sci & Engn, Kaifeng 475004, Peoples R China.

年份：2020

卷号：527

外文期刊名：APPLIED SURFACE SCIENCE

收录：;WOS:【SCI-EXPANDED(收录号:WOS:000564454600010)】；

基金：This work is supported by the National Natural Science Foundation of China (Grant No. 11704005), the Program for Science & Technology Innovation Talents in Universities of Henan Province (Grant No. 20HASTIT028) and the Science and Technology Breakthrough Project of Henan Province (No. 202102210199).

语种：英文

外文关键词：Oxygen reduction reaction; First-principles calculation; Metal-free catalyst; Boron-doped C9N4 monolayer

摘要：Replacing precious Pt-based catalysts with cheap metal-free catalysts would make the hydrogen economy viable. Herein, based on first-principles calculations, we have systemically investigated the oxygen reduction reaction (ORR) under the acid environment catalyzed by the B-doped C9N4 monolayer, a nodal-line semimetal. It is found that the doped B atom energetically prefers to replace the inner C atom with an exothermicity of 0.89 eV, and the resulting B-doped C9N4 retains the metallic conductivity beneficial for the charge transfer during the electrocatalytic process. The ORR prefers to adopt efficient four-electron pathways by firstly forming two energetically almost degenerate OOH species (OOH alpha and OOH beta). For further hydrogenation reactions, the formations of OH + OH and H2O + OH with similar energy barriers of about 1.0 eV are the rate-determining steps for OOH alpha and OOH beta configurations, respectively. Moreover, for both ORR pathways the potential-determining step is the last electron-proton pair transfer reaction with an overpotential of 0.98 V. Electronic structure analysis shows that due to the small electronegativity of the B atom, O-2 can be effectively activated by charge transfer and further orbital hybridization, which initiates the ORR. Present study suggests that the metal-free B-doped C9N4 monolayer has great potential application for ORR.