Modulating Fe spin state in FeNC catalysts by adjacent Fe atomic clusters to facilitate oxygen reduction reaction in proton exchange membrane fuel cell

被引：32

作者：

Chen, Chengjie ^{[1
]}

Wu, Yinlong ^{[1
]}

Li, Xiulan ^{[1
]}

Ye, Yanting ^{[1
]}

Li, Zilong ^{[1
]}

Zhou, Yifan ^{[2
]}

Chen, Jian ^{[2
]}

Yang, Muzi ^{[2
]}

Xie, Fangyan ^{[2
]}

Jin, Yanshuo ^{[1
]}

Jones, Colton ^{[3
]}

Wang, Nan ^{[1
]}

Meng, Hui ^{[1
]}

Chen, Shaowei ^{[3
]}

机构：

[1] Jinan Univ, Guangdong Prov Engn Technol Res Ctr Vacuum Coating, Dept Phys,Guangzhou Key Lab Vacuum Coating Technol, Guangdong Prov Key Lab Opt Fiber Sensing & Commun,, Guangzhou 510632, Guangdong, Peoples R China

[2] Sun Yat Sen Univ, Instrumental Anal & Res Ctr, Guangzhou 510275, Guangdong, Peoples R China

[3] Univ Calif Santa Cruz, Dept Chem & Biochem, 1156 High St, Santa Cruz, CA 95064 USA

来源：

APPLIED CATALYSIS B-ENVIRONMENT AND ENERGY | 2024年 / 342卷

基金：

中国国家自然科学基金; 美国国家科学基金会;

关键词：

Single atom site; Few-atom cluster; Spin state; Oxygen reduction reaction; Proton exchange membrane fuel cell; GENERALIZED GRADIENT APPROXIMATION; POROUS CARBONS; ELECTROCATALYST; PERFORMANCE; SITES;

D O I：

10.1016/j.apcatb.2023.123407

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Iron,nitrogen-codoped carbon (FeNC) has emerged as promising alternatives to precious metals for oxygen reduction reaction (ORR). Herein, we demonstrate that the ORR activity of FeNC can be markedly enhanced by the incorporation of adjacent Fe few-atom clusters (FeAC), where the octahedral field of FeAC boosts the splitting of the parallelogram field of FeN4, and facilitates the transition from high-spin (t2g 3 eg 2) Fe(III)N4 to medium-spin (t2g 5 eg 1) Fe(II)N4 and hence the interaction with the pi* antibonding orbitals of oxygen. This leads to a remarkable ORR performance due to optimized desorption of the OH* intermediate on FeN4, with a half-wave potential of +0.80 in 0.1 M HClO4, in comparison to that with only FeN4 single-atom moieties. In H2-O2 fuel cell tests, a high peak power density of 0.80 W cm-2 is obtained. Results from this work highlight the significance of spin en-gineering in the manipulation and optimization of the ORR activity of single-atom catalysts.

引用

页数：11

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