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Research Article | Open Access

Fe atoms anchored on defective nitrogen doped hollow carbon spheres as efficient electrocatalysts for oxygen reduction reaction

Panpan Su1,2,§, Wenjuan Huang1,2,§, Jiangwei Zhang2,3,§, Utsab Guharoy2,4, Qinggang Du1,2, Qiao Sun4, Qike Jiang3,5, Yi Cheng6,7, Jie Yang1( ), Xiaoli Zhang8, Yongsheng Liu1, San Ping Jiang7, Jian Liu2,7,9( )
College of Mathematics and Physics, Shanghai University of Electric Power, Shanghai 200090, China
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
State Key Laboratory of Radiation Medicine and Protection, Collaborative Innovation Center of Radiation Medicine of Jiangsu Higher Education Institutions, School for Radiological and Interdisciplinary Sciences, Soochow University, Suzhou 215123, China
Division of Energy Research Resources, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
Department of Environmental Engineering, School of Metallurgy and Environment, Central South University, Changsha 410083, China
WA School of Mines: Minerals, Energy and Chemical Engineering, Curtin University, Perth, WA 6102, Australia
State Centre for International Cooperation on Designer Low-Carbon & Environmental Materials, School of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450001, China
DICP-Surrey Joint Centre for Future Materials, Department of Chemical and Process Engineering, University of Surrey, Guildford, Surrey, UK

§ Panpan Su, Wenjuan Huang, and Jiangwei Zhang contributed equally to this work.

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Graphical Abstract

Abstract

Defective electrocatalysts, especially for intrinsic defective carbon, have aroused a wide concern owing to high spin and charge densities. However, the designated nitrogen species favorable for creating defects by the removal of nitrogen, and the influence of defects for the coordination structure of active site and oxygen reduction reaction (ORR) activity have not been elucidated. Herein, we designed and synthesized a pair of electrocatalysts, denoted as Fe-N/C and Fe-ND/C for coordination sites of atomic iron-nitrogen and iron-nitrogen/defect configuration embedded in hollow carbon spheres, respectively, through direct pyrolysis of their corresponding hollow carbon spheres adsorbed with Fe(acac)3. The nitrogen defects were fabricated via the evaporation of pyrrolic-N on nitrogen doped hollow carbon spheres. Results of comparative experiments between Fe-N/C and Fe-ND/C reveal that Fe-ND/C shows superior ORR activity with an onset potential of 30 mV higher than that of Fe-N/C. Fe-ND sites are more favorable for the enhancement of ORR activity. Density functional theory (DFT) calculation demonstrates that Fe-ND/C with proposed coordination structure of FeN4−x (0<x<4) anchored by OH as axial ligand during ORR, weakens the strong binding of OH* intermediate and promotes the desorption of OH* as rate-determining step for ORR in alkaline electrolyte. Thus, Fe-ND/C electrocatalysts present much better ORR activity compared with that of Fe-N/C with proposed coordination structure of FeN4.

Keywords

atomic ironnitrogen defectcoordination environmenthollow carbon spheresoxygen reduction reaction

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Nano Research
Volume 14 Issue 4,
April 2021
Pages 1069-1077
DOI: 10.1007/s12274-020-3151-8
Cite this article:
Su P, Huang W, Zhang J, et al. Fe atoms anchored on defective nitrogen doped hollow carbon spheres as efficient electrocatalysts for oxygen reduction reaction. Nano Research, 2021, 14(4): 1069-1077. https://doi.org/10.1007/s12274-020-3151-8
Topics:
Nano unitCarbonCoordination reactionsDefectsDensity functional theoryDoping (additives)ElectrocatalystsElectrolysis ElectrolytesElectrolytic reduction IronNitrogenOxygenSpheres

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Received: 24 June 2020
Revised: 22 September 2020
Accepted: 30 September 2020
Published: 18 November 2020
© The Author(s) 2020

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