Regulating the FeN4 Moiety by Constructing Fe-Mo Dual-Metal Atom Sites for Efficient Electrochemical Oxygen Reduction

Peng Zhu; Xiang Xiong; Xiaolu Wang; Chenliang Ye; Jiazhan Li; Wenming Sun; Xiaohui Sun; Jingjing Jiang; Zhongbin Zhuang; Dingsheng Wang; Yadong Li

doi:10.1021/acs.nanolett.2c03623

Regulating the FeN₄ Moiety by Constructing Fe-Mo Dual-Metal Atom Sites for Efficient Electrochemical Oxygen Reduction

Nano Lett. 2022 Dec 14;22(23):9507-9515. doi: 10.1021/acs.nanolett.2c03623. Epub 2022 Nov 15.

Authors

Peng Zhu¹, Xiang Xiong², Xiaolu Wang¹, Chenliang Ye³, Jiazhan Li¹, Wenming Sun⁴, Xiaohui Sun¹, Jingjing Jiang¹, Zhongbin Zhuang⁵, Dingsheng Wang¹, Yadong Li^{1

6

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Affiliations

¹ Department of Chemistry, Tsinghua University, Beijing 100084, People's Republic of China.
² Powder Metallurgy Research Institute and State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083, People's Republic of China.
³ College of Materials Science and Engineering, Shenzhen University, Shenzhen 518060, People's Republic of China.
⁴ Department of Chemistry, Beijing Key Laboratory for Optical Materials and Photonic Devices, Capital Normal University, Beijing 100048, People's Republic of China.
⁵ State Key Lab of Organic-Inorganic Composites and Beijing Key Laboratory of Energy Environmental Catalysis, Beijing University of Chemical Technology, Beijing 100029, People's Republic of China.
⁶ College of Chemistry, Beijing Normal University, Beijing 100875, People's Republic of China.
⁷ Key Laboratory of Functional Molecular Solids, Ministry of Education, College of Chemistry and Materials Science, Anhui Normal University, Wuhu 241002, People's Republic of China.

PMID: 36378069
DOI: 10.1021/acs.nanolett.2c03623

Abstract

An Fe-N-C catalyst with an FeN₄ active moiety has gained ever-increasing attention for the oxygen reduction reaction (ORR); however, the catalytic performance is sluggish in acidic solutions and the regulation is still a challenge. Herein, Fe-Mo dual-metal sites were constructed to tune the ORR activity of a mononuclear Fe site embedded in porous nitrogen-doped carbon. The cracking of O-O bonds is much more facile on the Fe-Mo atomic pair site due to the preferred bridge-cis adsorption model of oxygen molecules. The downshift of the Fe d band center when an Mo atom is introduced to the FeN_x configuration optimizes the absorption-desorption behavior of ORR intermediates in the FeMoN₆ active moiety, thus boosting the catalytic performance. The construction of dual-metal atom sites to regulate the catalytically active moiety paves the way for boosting the electrocatalytic performance of other similar non-precious-metal catalysts.

Keywords: active moiety; atomic sites; electrocatalyst; metal−N−C; oxygen reduction reaction.