Fabricating high-loading Fe-N4 single-atom catalysts for oxygen reduction reaction by carbon-assisted pyrolysis of metal complexes

doi:10.1016/S1872-2067(20)63689-0

Abstract

Abstract:

Iron-based single-atom catalysts with nitrogen-doped carbon as support (Fe-SA/NPC) are considered effective alternatives to replace Pt-group metals for scalable application in fuel cells. However, synthesizing high-loading Fe-SA catalysts by a simple procedure remains challenging. Herein, we report a high-loading (7.5 wt%) Fe-SA/NPC catalyst prepared by carbon-assisted pyrolysis of metal complexes. Both the nitrogen-doped porous carbon (NPC) support with high specific surface area and ο-phenylenediamine (o-PD) play key roles role in the preparation of high-loading Fe-SA/NPC catalysts. The results of X-ray photoelectron spectroscopy, high-angle annular dark-field scanning transmission electron microscopy, and X-ray absorption fine structure spectroscopy experiments show that the Fe atoms are anchored on the carbon carriers in a single-atom site configuration and coordinated with four of the doped nitrogen atoms of the carbon substrates (Fe-N₄). The activities of the Fe-SA/NPC catalysts in the oxygen reduction reaction increased with increasing iron loading. The optimized 250Fe-SA/NPC-800 catalyst exhibited an onset potential 0.97 V of and a half-wave potential of 0.85 V. Our study provides a simple approach for the large-scale synthesis of high-loading single-atom catalysts.

Key words: Fe-N₄ single-atom catalysts, Oxygen reduction reaction, High-loading, Coordinated effect, Four-electron transfer process

Jun-Sheng Jiang, He-Lei Wei, Ai-Dong Tan, Rui Si, Wei-De Zhang, Yu-Xiang Yu. Fabricating high-loading Fe-N₄ single-atom catalysts for oxygen reduction reaction by carbon-assisted pyrolysis of metal complexes[J]. Chinese Journal of Catalysis, 2021, 42(5): 753-761.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(20)63689-0

https://www.cjcatal.com/EN/Y2021/V42/I5/753

Figures/Tables 11

Scheme 1. Schematic illustration of the formation of xFe-SA/NPC-T samples; yellow and blue-grey balls represent melamine and the Fe-o-PD complex, respectively.

Fig. 1. XRD patterns (A) and Raman spectra (B) of NPC, xFe-SA/NPC-800, and 375Fe-NP/NPC-800 samples.

Fig. 2. Morphology characterization of 250Fe-SA/NPC-800 sample. (A) SEM image; (B) TEM image; (C) High-resolution AC-HAADF-STEM image; (D) Low-resolution AC-HAADF-STEM image with corresponding EDX mapping.

Fig. 3. XPS spectra of 250Fe-SA/NPC-800. (A) XPS survey spectrum; (B) High-resolution C 1s spectrum; (C) High-resolution N 1s spectrum; (D) High-resolution Fe 2p spectrum.

Fig. 4. XAFS profiles of 250Fe-SA/NPC-800 catalyst. (A) Fe K-edge XANES profiles of 250Fe-SA/NPC-800 catalyst and reference samples; (B) Corresponding EXAFS fitting curves in R-space, with the inset showing a schematic model.

Fig. 5. ORR performance. (A) RDE polarization curves of the samples; (B) Onset and half-wave potentials of the samples (a = NPC, b = 100Fe-SA/NPC-800, c: 175Fe-SA/NPC-800, d: 250Fe-SA/NPC-800, e: 375Fe-NP/NPC-800); (C) LSV polarization curves of 250Fe-SA/NPC-800 with different rotation speeds (400-2025 rpm); (D) K-L plots of 250Fe-SA/NPC-800.

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Fabricating high-loading Fe-N₄ single-atom catalysts for oxygen reduction reaction by carbon-assisted pyrolysis of metal complexes

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