Phosphorus and nitrogen co-doped-graphene: Stability and catalytic activity in oxygen reduction reaction
Jinmin Guo,
Weiwei Shao,
Hongfeng Yan,
Manhong Zhao,
Yang-Yi Liu,
Qiufeng Fang,
Tianle Xia,
Jinlong Wang,
Xiao-Chun Li
Affiliations
Jinmin Guo
School of Electronic Engineering, Tongling University, Tongling, People’s Republic of China
Weiwei Shao
School of Electronic Engineering, Tongling University, Tongling, People’s Republic of China
Hongfeng Yan
School of Electronic Engineering, Tongling University, Tongling, People’s Republic of China
Manhong Zhao
School of Electronic Engineering, Tongling University, Tongling, People’s Republic of China
Yang-Yi Liu
School of Electronic Engineering, Tongling University, Tongling, People’s Republic of China
Qiufeng Fang
School of Electronic Engineering, Tongling University, Tongling, People’s Republic of China
Tianle Xia
School of Electronic Engineering, Tongling University, Tongling, People’s Republic of China
Jinlong Wang
School of Electronic Engineering, Tongling University, Tongling, People’s Republic of China; Institute of plasma physics, HFIPS, Chinese Academy of Sciences, Hefei, People’s Republic of China; Corresponding author at: School of Electronic Engineering, Tongling University, Tongling, People’s Republic of China.
Xiao-Chun Li
Institute of plasma physics, HFIPS, Chinese Academy of Sciences, Hefei, People’s Republic of China; Corresponding author.
This study systematically investigated the stable configurations and oxygen reduction reaction (ORR) catalytic activity of PN co-doped graphene using first-principles methods. We found that PN co-doped graphene substrates are generally highly stable. The adsorption energy of adsorbates is linearly positively correlated with the number of electrons obtained from the substrate. The P atoms serve as catalytic activity sites, the co-doping of N significantly enhances the adsorption energies of intermediate species in the ORR process, facilitating the direct dissociation of O2 and O2H. The solvation effect has a non-negligible impact on the adsorption energy of adsorbates, especially for O2. Due to the excessive adsorption of O, it poisons and inhibits the catalytic activity of P active sites for ORR. However, after O adsorption, the C atoms neighboring the PN impurity atoms in the P-Nn-Gra (n=2,3) substrates exhibit better catalytic activity than that of graphene doped with P/N alone. The P-Nn-defect-Gra (n=2,3,4) substrates are potential catalysts with good HER catalytic activity.
