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]; Shen, Jiansheng[1]; Lu, Zhansheng[3]; Ma, Dongwei[2]

第一作者：He, Bingling;赫丙玲

通讯作者：Ma, Dongwei

机构：[1] College of Physics and Electronic Engineering, Xinxiang University, Xinxiang, 453003, China; [2] Key Laboratory for Special Functional Materials of Ministry of Education, and School of Materials Science and Engineering, Henan University, Kaifeng, 475004, China; [3] College of Physics, Henan Normal University, Xinxiang, 453007, China

第一机构：新乡学院物理与电子工程学院

通讯机构：[2]Key Laboratory for Special Functional Materials of Ministry of Education, and School of Materials Science and Engineering, Henan University, Kaifeng, 475004, China

年份：2020

卷号：527

外文期刊名：Applied Surface Science

收录：EI(收录号：20202408811920);Scopus(收录号：2-s2.0-85086066308)

语种：英文

外文关键词：Atoms - Boron - Calculations - Catalysts - Charge transfer - Chemical bonds - Electrolytic reduction - Electronegativity - Electronic structure - Hydrogen economy - Hydrogenation - Metals - Monolayers - Orbital transfer - Oxygen

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 (OOHα and OOHβ). 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 OOHα and OOHβ 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, O2 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. ? 2020 Elsevier B.V.