Construction of N, P Co-Doped Carbon Frames Anchored with Fe Single Atoms and Fe2 P Nanoparticles as a Robust Coupling Catalyst for Electrocatalytic Oxygen Reduction

Yuan Pan; Xuelu Ma; Minmin Wang; Xuan Yang; Shoujie Liu; Hsiao-Chien Chen; Zeweng Zhuang; Yanhui Zhang; Weng-Chon Cheong; Chao Zhang; Xing Cao; Rongan Shen; Qian Xu; Wei Zhu; Yunqi Liu; Xingdong Wang; Xuejiang Zhang; Wensheng Yan; Jun Li; Hao Ming Chen; Chen Chen; Yadong Li

doi:10.1002/adma.202203621

Construction of N, P Co-Doped Carbon Frames Anchored with Fe Single Atoms and Fe₂ P Nanoparticles as a Robust Coupling Catalyst for Electrocatalytic Oxygen Reduction

Adv Mater. 2022 Jul;34(29):e2203621. doi: 10.1002/adma.202203621. Epub 2022 Jun 16.

Authors

Yuan Pan^{1

2}, Xuelu Ma³, Minmin Wang¹, Xuan Yang⁴, Shoujie Liu², Hsiao-Chien Chen⁵, Zeweng Zhuang², Yanhui Zhang⁶, Weng-Chon Cheong², Chao Zhang², Xing Cao², Rongan Shen², Qian Xu⁷, Wei Zhu⁸, Yunqi Liu¹, Xingdong Wang⁸, Xuejiang Zhang⁸, Wensheng Yan⁷, Jun Li², Hao Ming Chen⁹, Chen Chen², Yadong Li²

Affiliations

¹ State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao, 266580, China.
² Department of Chemistry, Tsinghua University, Beijing, 100084, China.
³ School of Chemical and Environmental Engineering, China University of Mining and Technology, Beijing, 100083, China.
⁴ School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan, 430074, China.
⁵ Center for Reliability Science and Technologies, Chang Gung University, Taoyuan, 33302, Taiwan.
⁶ School of Materials Science and Engineering, Key Laboratory for Anisotropy and Texture of Materials, Ministry of Education, Northeastern University, Shenyang, 110819, China.
⁷ National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, Anhui, 230029, China.
⁸ State Key Lab of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing, 100029, China.
⁹ Department of Chemistry, National Taiwan University, Taipei, 106, Taiwan.

PMID: 35606157
DOI: 10.1002/adma.202203621

Abstract

A coupling catalyst of highly dispersed N, P co-doped carbon frames (NPCFs) anchored with Fe single atoms (SAs) and Fe₂ P nanoparticles (NPs) is synthesized by a novel in situ doping-adsorption-phosphatization strategy for the electrocatalytic oxygen reduction reaction (ORR). The optimized Fe SAs-Fe₂ P NPs/NPCFs-2.5 catalyst shows a superior ORR activity and stability in 0.5 m H₂ SO₄ and 0.1 m KOH, respectively. Theoretical calculations reveal a synergistic effect, in that the existence of Fe₂ P weakens the adsorption of ORR intermediates on active sites and lowers the reaction free energy. The doped P atoms with a strong electron-donating ability elevate the energy level of Fe-3d orbitals and facilitate the adsorption of O₂ . The active Fe atoms exist in a low oxidation state and are less positively charged, and they serve as an electron reservoir capable of donating and releasing electrons, thus improving the ORR activity. Operando and in situ characterization results indicate that the atomically dispersed FeN₄ /FeP coupled active centers in the Fe SAs-Fe₂ P NPs/NPCFs-2.5 catalyst are characteristic of the different catalytic mechanisms in acidic and alkaline media. This work proposes a novel idea for constructing coupling catalysts with atomic-level precision and provides a strong reference for the development of high-efficiency ORR electrocatalysts for practical application.

Keywords: coupling catalysts; electrocatalysis; oxygen reduction reaction; single-atom catalysts.

Abstract

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