Unraveling the Electron Transfer Effect of Single-Metal Ce-N4 Sites via Mesopore-Coupling for Boosted Oxygen Reduction Activity

Jianping Liu; Chaozhong Guo; Lingtao Sun; Yao Liu; Hongdian Chen; Chenyang Shu; Jiangyou Dai; Chuanlan Xu; Rong Jin; Honglin Li; Yujun Si

doi:10.1002/smll.202305615

Unraveling the Electron Transfer Effect of Single-Metal Ce-N₄ Sites via Mesopore-Coupling for Boosted Oxygen Reduction Activity

Small. 2024 Jan;20(4):e2305615. doi: 10.1002/smll.202305615. Epub 2023 Sep 17.

Authors

Jianping Liu^{1

2}, Chaozhong Guo¹, Lingtao Sun^{1

3}, Yao Liu¹, Hongdian Chen², Chenyang Shu², Jiangyou Dai¹, Chuanlan Xu⁴, Rong Jin^{1

3}, Honglin Li⁵, Yujun Si⁶

Affiliations

¹ Chongqing Key Laboratory of Materials Surface & Interface Science, Chongqing University of Arts and Sciences, Chongqing, 402160, China.
² School of Chemistry and Chemical Engineering, Chongqing University of Technology, Chongqing, 400054, China.
³ Institute of Chemical and Gas and Oil Technologies, T.F. Gorbachev Kuzbass State Technical University, Kemerovo, 650000, Russia.
⁴ College of Chemistry and Chemical Engineering, Chongqing University, Chongqing, 401331, China.
⁵ School of Physics and Electronic Engineering, Chongqing Normal University, Chongqing, 401331, China.
⁶ College of Chemistry and Environmental Engineering, Sichuan University of Science and Engineering, Zigong, 643000, China.

PMID: 37718453
DOI: 10.1002/smll.202305615

Abstract

The development of cerium (Ce) single-atom (SA) electrocatalysts for oxygen reduction reaction (ORR) with high active-site utilization and intrinsic activity has become popular recently but remains challenging. Inspired by an interesting phenomenon that pore-coupling with single-metal cerium sites can accelerate the electron transfer predicted by density functional theory calculations, here, a facile strategy is reported for directional design of a highly active and stable Ce SA catalyst (Ce SA/MC) by the coupling of single-metal Ce-N₄ sites and mesopores in nanocarbon via pore-confinement-pyrolysis of Ce/phenanthroline complexes combined with controlling the formation of Ce oxides. This catalyst delivers a comparable ORR catalytic activity with a half-wave potential of 0.845 V versus RHE to the Pt/C catalyst. Also, a Ce SA/MC-based zinc-air battery (ZAB) has exhibited a higher energy density (924 Wh kg_Zn ^-1 ) and better long-term cycling durability than a Pt/C-based ZAB. This proposed strategy may open a door for designing efficient rare-earth metal catalysts with single-metal sites coupling with porous structures for next-generation energy devices.

Keywords: electron transfer; mesopore-coupling; oxygen reduction; single-metal Ce-N4 sites.

Abstract

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