Axial Chlorine Induced Electron Delocalization in Atomically Dispersed FeN4 Electrocatalyst for Oxygen Reduction Reaction with Improved Hydrogen Peroxide Tolerance

Author:

Sabhapathy Palani1ORCID,Raghunath Puttikam2,Sabbah Amr134,Shown Indrajit5,Bayikadi Khasim Saheb3,Xie Rui‐Kun6,Krishnamoorthy Vimal7,Lin Ming‐Chang2,Chen Kuei‐Hsien13,Chen Li‐Chyong189ORCID

Affiliation:

1. Center for Condensed Matter Sciences National Taiwan University Taipei 10617 Taiwan

2. Department of Applied Chemistry National Yang‐Ming Chiao‐Tung University Hsinchu 30010 Taiwan

3. Institute of Atomic and Molecular Sciences Academia Sinica Taipei 10617 Taiwan

4. Tabbin Institute for Metallurgical Studies Tabbin, Helwan 109 Cairo 11421 Egypt

5. Department of Chemistry Hindustan Institute of Technology and Sciences Chennai 603103 India

6. National Synchrotron Radiation Research Center Hsinchu 30076 Taiwan

7. Graduate Institute of Applied Science and Technology National Taiwan University of Science and Technology Taipei 10607 Taiwan

8. Center of Atomic Initiative for New Materials National Taiwan University Taipei 10617 Taiwan

9. Department of Physics National Taiwan University Taipei 10617 Taiwan

Abstract

AbstractAtomically dispersed iron sites on nitrogen‐doped carbon (Fe‐NC) are the most active Pt‐group‐metal‐free catalysts for oxygen reduction reaction (ORR). However, due to oxidative corrosion and the Fenton reaction, Fe‐NC catalysts are insufficiently active and stable. Herein, w e demonstrated that the axial Cl‐modified Fe‐NC (Cl‐Fe‐NC) electrocatalyst is active and stable for the ORR in acidic conditions with high H2O2 tolerance. The Cl‐Fe‐NC exhibits excellent ORR activity, with a high half‐wave potential (E1/2) of 0.82 V versus a reversible hydrogen electrode (RHE), comparable to Pt/C (E1/2 = 0.85 V versus RHE) and better than Fe‐NC (E1/2 = 0.79 V versus RHE). X‐ray absorption spectroscopy analysis confirms that chlorine is axially integrated into the FeN4. More interestingly, compared to Fe‐NC, the Fenton reaction is markedly suppressed in Cl‐Fe‐NC. In situ electrochemical impedance spectroscopy reveals that Cl‐Fe‐NC provides efficient electron transfer and faster reaction kinetics than Fe‐NC. Density functional theory calculations reveal that incorporating Cl into FeN4 can drive the electron density delocalization of the FeN4 site, leading to a moderate adsorption free energy of OH* (∆GOH*), d‐band center, and a high onset potential, and promotes the direct four‐electron‐transfer ORR with weak H2O2 binding ability compared to Cl‐free FeN4, indicating superior intrinsic ORR activity.

Funder

Ministry of Science and Technology

National Taiwan University

Ministry of Education

Department of Science and Technology, Government of Kerala

Science and Engineering Research Board

Publisher

Wiley

Subject

Biomaterials,Biotechnology,General Materials Science,General Chemistry

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