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The Asymmetrical Fe-O-Se Bonds in Fe 2 O(SeO 3 ) 2 Boosting Bifunctional Oxygen Electrocatalytic Performance for Zinc-Air Battery.

Authors :
Xu HM
Yue KH
Song LJ
Zhang HC
Zhu HR
Zhang ZJ
Li GR
Source :
Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2024 Sep 03, pp. e202412025. Date of Electronic Publication: 2024 Sep 03.
Publication Year :
2024
Publisher :
Ahead of Print

Abstract

Zinc-air batteries (ZABs) have the advantages of high energy density and rich zinc raw materials. It is a low-cost, green and sustainable energy storage device. At present, one of the key technologies that hinder the large-scale application of ZABs is the design and fabrication oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) bifunctional catalysts with excellent performance, especially the non-platinum-based catalysts. Here N-doped carbon-coated Fe-based selenium oxide catalyst Fe <subscript>2</subscript> O(SeO <subscript>3</subscript> ) <subscript>2</subscript> /Fe <subscript>3</subscript> C@NC with high performance has been fabricated by a one-step pyrolysis and then the electrochemical oxidization. The experimental results confirmed that the existence of Fe-O-Se bonds in Fe <subscript>2</subscript> O(SeO <subscript>3</subscript> ) <subscript>2</subscript> crystal phase of Fe <subscript>2</subscript> O(SeO <subscript>3</subscript> ) <subscript>2</subscript> /Fe <subscript>3</subscript> C@NC, and the Fe-O-Se bonds could obviously enhance ORR and OER catalytic performance of Fe <subscript>2</subscript> O(SeO <subscript>3</subscript> ) <subscript>2</subscript> /Fe <subscript>3</subscript> C@NC. Density functional theoretical calculations (DFT) confirmed that the Fe <subscript>2</subscript> O(SeO <subscript>3</subscript> ) <subscript>2</subscript> in Fe <subscript>2</subscript> O(SeO <subscript>3</subscript> ) <subscript>2</subscript> /Fe <subscript>3</subscript> C@NC had a higher d-band center of Fe atom and a lower p-orbital coupling degree with its own lattice O atom than Fe <subscript>2</subscript> O <subscript>3</subscript> , which leads to Fe site of Fe <subscript>2</subscript> O(SeO <subscript>3</subscript> ) <subscript>2</subscript> being more likely to adsorb external oxygen intermediates. The Fe-O-Se bonds in Fe <subscript>2</subscript> O(SeO <subscript>3</subscript> ) <subscript>2</subscript> results in the modification of coordination environment of Fe atoms and optimizes the adsorption energy of Fe site for oxygen intermediates. Compared with Fe <subscript>2</subscript> O <subscript>3</subscript> /Fe <subscript>3</subscript> C@NC, the Fe <subscript>2</subscript> O(SeO <subscript>3</subscript> ) <subscript>2</subscript> /Fe <subscript>3</subscript> C@NC showed the obvious enhancements of ORR/OER catalytic activities with a half-wave potential of 0.91 V for ORR in 0.1 M KOH electrolyte and a low overpotential of 345 mV for OER at 10 mA cm <superscript>-2</superscript> in a 1.0 M KOH electrolyte. The peak power density and specific capacity of Fe <subscript>2</subscript> O(SeO <subscript>3</subscript> ) <subscript>2</subscript> /Fe <subscript>3</subscript> C@NC-based ZABs are higher than those of Pt/C+RuO <subscript>2</subscript> -ZABs. The above results demonstrate that the asymmetrical Fe-O-Se bonds in Fe <subscript>2</subscript> O(SeO <subscript>3</subscript> ) <subscript>2</subscript> plays a key role in improving the bifunctional catalytic activities of ORR/OER for ZABs.<br /> (© 2024 Wiley-VCH GmbH.)

Details

Language :
English
ISSN :
1521-3773
Database :
MEDLINE
Journal :
Angewandte Chemie (International ed. in English)
Publication Type :
Academic Journal
Accession number :
39228013
Full Text :
https://doi.org/10.1002/anie.202412025