Probing the catalytic activity of M-N4−xOx embedded graphene for the oxygen reduction reaction by density functional theory

doi:10.1007/s11705-020-2017-7

Front. Chem. Sci. Eng.

2021, Vol. 15

Issue (5) : 1206-1216 https://doi.org/10.1007/s11705-020-2017-7

RESEARCH ARTICLE

Probing the catalytic activity of M-N₄₋_xO_x embedded graphene for the oxygen reduction reaction by density functional theory

Fan Ge^1,³, Qingan Qiao², Xin Chen^1,^3,⁴(

), You Wu¹

¹. State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, Southwest Petroleum University, Chengdu 610500, China
². School of Chemistry and Materials Science, Ludong University, Yantai 264025, China
³. Center for Computational Chemistry and Molecular Simulation, College of Chemistry and Chemical Engineering, Southwest Petroleum University, Chengdu 610500, China
⁴. Oil & Gas Field Applied Chemistry Key Laboratory of Sichuan Province, College of Chemistry and Chemical Engineering, Southwest Petroleum University, Chengdu 610500, China

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Abstract

In this work, the detailed oxygen reduction reaction (ORR) catalytic performance of M-N₄₋_xO_x (M= Fe, Co, and Ni; x = 1–4) has been explored via the detailed density functional theory method. The results suggest that the formation energy of M-N₄₋_xO_x shows a good linear relationship with the number of doped O atoms. The adsorption manner of O₂ on M-N₄₋_xO_x changed from end-on (x = 1 and 2) to side-on (x = 3 and 4), and the adsorption strength gradually increased. Based on the results for binding strength of ORR intermediates and the Gibbs free energy of ORR steps on the studied catalysts, we screened out two highly active ORR catalysts, namely Co-N₃O₁ and Ni-N₂O₂, which possess very small overpotentials of 0.27 and 0.32 V, respectively. Such activities are higher than the precious Pt catalyst. Electronic structure analysis reveals one of the reasons for the higher activity of Co-N₃O₁ and Ni-N₂O₂ is that they have small energy gaps and moderate highest occupied molecular orbital energy levels. Furthermore, the results of the density of states reveal that the O doping can improve the electronic structure of the original catalyst to tune the adsorption of the ORR intermediates.

Keywords M-N-C catalyst oxygen doping oxygen reduction reaction catalytic activity density functional theory

Corresponding Author(s): Xin Chen

Just Accepted Date: 31 December 2020 Online First Date: 05 February 2021 Issue Date: 30 August 2021

Cite this article:

Fan Ge,Qingan Qiao,Xin Chen, et al. Probing the catalytic activity of M-N₄₋_xO_x embedded graphene for the oxygen reduction reaction by density functional theory[J]. Front. Chem. Sci. Eng., 2021, 15(5): 1206-1216.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-020-2017-7
https://academic.hep.com.cn/fcse/EN/Y2021/V15/I5/1206

Fig.1 Top and side views of geometry structure of (a) M-N₃O₁, (b) M-N₂O₂, (c) M-N₁O₃, and (d) M-O₄ (M= Fe, Co, and Ni).

Fig.2 Variations of formation energies with the number of O atoms and the doping type of metal atoms.

Fig.3 Optimized adsorption configurations of O₂ on (a) Fe-N₄₋_xO_x, (b) Co-N₄₋_xO_x, and (c) Ni-N₄₋_xO_x (x = 1–4).

Fig.4 E_ads of O₂ on M-N₄₋_xO_x (x = 1–4).

Fig.5 Difference values between the binding energy of ORR intermediates on M-N₄₋_xO_x (x = 1 and 2) and that on the Pt(111).

Fig.6 Optimized binding configurations of ORR intermediates (OOH, O, and OH) on (a) Fe-N₃O₁, (b) Fe-N₂O₂, (c) Co-N₃O₁, (d) Co-N₂O₂, (e) Ni-N₃O₁, and (f) Ni-N₂O₂.

Tab.1 The adsorption free energies^a) of O, OH, and OOH on M-N₄₋_xO_x (M= Fe, Co, and Ni; x = 1−4)

Fig.7 Scaling relationship between DG_*_OH and DG_*_OOH, DG_*_O.

Fig.8 Free energy diagram of ORR pathways on (a) M-N₃O₁ and (b) M-N₂O₂.

Tab.2 HOMO, LUMO, and E_g of M-N₄₋_xO_x (x = 1 and 2)^a)

Fig.9 The DOS of O adsorbed on (a) Co-N₃O₁, (b) Co-N₂O₂, (c) Co-N₁O₃, and (d) Co-O₄.

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