Graphdiyne doped with sp-hybridized nitrogen atoms at acetylenic sites as potential metal-free electrocatalysts for oxygen reduction reaction

Zhen Feng; Yaqiang Ma; Yi Li; Renyi Li; Jing Liu; Huiting Li; Yanan Tang; Xianqi Dai

doi:10.1088/1361-648X/ab3350

Graphdiyne doped with sp-hybridized nitrogen atoms at acetylenic sites as potential metal-free electrocatalysts for oxygen reduction reaction

J Phys Condens Matter. 2019 Nov 20;31(46):465201. doi: 10.1088/1361-648X/ab3350. Epub 2019 Jul 18.

Authors

Zhen Feng¹, Yaqiang Ma, Yi Li, Renyi Li, Jing Liu, Huiting Li, Yanan Tang, Xianqi Dai

Affiliation

¹ College of Physics and Materials Science, Henan Normal University, Xinxiang, Henan 453007, People's Republic of China. College of Materials Science and Engineering, Henan Institute of Technology, Xinxiang, Henan 453000, People's Republic of China.

PMID: 31318700
DOI: 10.1088/1361-648X/ab3350

Abstract

Exploring metal-free electrocatalysts with high efficiency and lower cost for oxygen reduction reaction (ORR) is necessary to realize the commercialization of fuel cells. In this paper, the ORR mechanisms on nitrogen-doped graphdiyne (GDY) are investigated using the first principles calculations. It is found that the GDY doped with sp-hybridized N at acetylenic sites can activate molecular oxygen (O₂). The kinetically most favorable reaction pathway is O₂ → OOH → O + H₂O → OH → H₂O, which is an efficient four-electron ORR process. The first reaction step O₂ → OOH is the rate determining step (RDS), and the energy barrier is 0.61 eV. The energy barrier of RDS is smaller than that of pure Pt (0.80 eV). Therefore, these results illustrate that sp-hybridized N-doped GDY is a promising carbon-based metal-free ORR catalyst.