Simultaneously Engineering the Coordination Environment and Pore Architecture of Metal-Organic Framework-Derived Single-Atomic Iron Catalysts for Ultraefficient Oxygen Reduction

Feng Liu; Lei Shi; Shaofeng Song; Kai Ge; Xiaopeng Zhang; Yingchun Guo; Dong Liu

doi:10.1002/smll.202102425

Simultaneously Engineering the Coordination Environment and Pore Architecture of Metal-Organic Framework-Derived Single-Atomic Iron Catalysts for Ultraefficient Oxygen Reduction

Small. 2021 Oct;17(40):e2102425. doi: 10.1002/smll.202102425. Epub 2021 Sep 8.

Authors

Feng Liu¹, Lei Shi¹, Shaofeng Song², Kai Ge², Xiaopeng Zhang³, Yingchun Guo⁴, Dong Liu¹

Affiliations

¹ State Key Laboratory of Organic-Inorganic Composites, Beijing Advanced Innovation Center for Soft Matter Science and Engineering, College of Chemical Engineering, College of Materials Science and Engineering, Beijing University of Chemical Technology, Beijing, 100029, China.
² Hebei Key Laboratory of Functional Polymers, Institute of Polymer Science and Engineering, School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin, 300130, China.
³ Institute for Materials Chemistry and Engineering, Kyushu University, Fukuoka, 819-0395, Japan.
⁴ Key Laboratory of Special Functional Materials for Ecological Environment and Information, Hebei University of Technology, Ministry of Education, Tianjin, 300130, China.

PMID: 34494368
DOI: 10.1002/smll.202102425

Abstract

Designing highly efficient and durable electrocatalysts that accelerate sluggish oxygen reduction reaction kinetics for fuel cells and metal-air batteries are highly desirable but challenging. Herein, a facile yet robust strategy is reported to rationally design single iron active centers synergized with local S atoms in metal-organic frameworks derived from hierarchically porous carbon nanorods (Fe/N,S-HC). The cooperative trithiocyanuric acid-based coating not only introduces S atoms that regulate the coordination environment of the active centers, but also facilitates the formation of a hierarchically porous structure. Benefiting from electronic modulation and architectural functionality, Fe/N,S-HC catalyst shows markedly enhanced ORR performance with a half-wave potential (E_1/2 ) of 0.912 V and satisfactory long-term durability in alkaline medium, outperforming those of commercial Pt/C. Impressively, Fe/N,S-HC-based Zn-air battery also presents outstanding battery performance and long-term stability. Both electrochemical experimental and density functional theoretical (DFT) calculated results suggest that the FeN₄ sites tailored with local S atoms are favorable for the adsorption/desorption of oxygen intermediate, resulting in lower activation energy barrier and ultraefficient oxygen reduction catalytic activity. This work provides an atomic-level combined with porous morphological-level insights into oxygen reduction catalytic property, promoting rational design and development of novel highly efficient single-atom catalysts for the renewable energy applications.

Keywords: architectural engineering; electronic structure modulation; metal-organic frameworks; oxygen reduction; single-atom Fe.