Synergy of staggered stacking confinement and microporous defect fixation for high-density atomic FeII-N4 oxygen reduction active sites

doi:10.1016/S1872-2067(21)63992-X

Abstract

Abstract:

The development of high-performance nonprecious metal catalysts (NPMCs) to supersede Pt-based catalysts for the oxygen reduction reaction (ORR) in polymer electrolyte membrane fuel cells is highly desirable but remains challenging. In this paper, we present a pyrolysis strategy for spatial confinement and active-site fixation using iron phthalocyanine (FePc), phthalocyanine (Pc) and Zn salts as precursors. In the obtained carbon-based NPMC with a hierarchically porous nanostructure of thin-layered carbon nanosheets, nearly 100% of the total Fe species are Fe^II-N₄ active sites. In contrast, pyrolyzing FePc alone forms Fe-based nanoparticles embedded in amorphous carbon with only 5.9% Fe^II-N₄ active sites. Both experimental characterization and density functional theory calculations reveal that spatial confinement through the staggered π-π stacking of Pc macrocycles effectively prevents the demetallation of Fe atoms and the formation of Fe-based nanoparticles via aggregation. Furthermore, Zn-induced microporous defects allow the fixation of Fe^II-N₄ active sites. The synergistic effect of staggered stacking confinement and microporous defect fixation results in a high density of atomic Fe^II-N₄ active sites that can enhance the ORR. The optimal Fe^II-N₄-C electrocatalyst outperforms a commercial Pt/C catalyst in terms of half-wave potential, methanol tolerance, and long-term stability in alkaline media. This modulation strategy can greatly advance efforts to develop high-performance NPMCs.

Key words: Oxygen reduction reaction, Synergy strategy, Staggered stacking confinement, Microporous defects fixation, Fe^II-N₄

Menghui Chen, Yongting Chen, Zhili Yang, Jin Luo, Jialin Cai, Joey Chung-Yen Jung, Jiujun Zhang, Shengli Chen, Shiming Zhang. Synergy of staggered stacking confinement and microporous defect fixation for high-density atomic Fe^II-N₄ oxygen reduction active sites[J]. Chinese Journal of Catalysis, 2022, 43(7): 1870-1878.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63992-X

https://www.cjcatal.com/EN/Y2022/V43/I7/1870

Figures/Tables 8

Scheme 1. Schematic illustration of the preparation procedure for the Fe-Nx-C catalyst (c-(FePc+Pc+ZnCl2)).

Fig. 1. SEM (a), TEM (b), AC-HAADF-STEM (c) and corresponding elemental mapping of C (red), N (peacock blue), and Fe (yellow), and high-resolution AC-HAADF-STEM images (d) of the c-(FePc+Pc+ZnCl2) catalyst. Note that the white dots indicated by yellow circles in (d) are Fe atoms.

Fig. 2. DFT calculations. (a) Possible structures of MPc combined with Pc. (b) binding energies of Fe and average Fe-N bond length. (c) HOMO and LUMO isosurfaces for the calculated FePc molecule and FePc+Pc configuration.

Fig. 3. XRD patterns (a), pore-size distributions and N2 adsorption-desorption isotherms (inset) (b), XPS survey spectra (c) and deconvoluted N1s spectra (d) for the c-FePc, c-(FePc+Pc) and c-(FePc+Pc+ZnCl2) catalysts.

Table 1 Surface N species contents ((at%)) in various catalysts, as determined by XPS analysis.

Sample	Total N	Pyridinic N	Metal-N_x	Pyrrolic N	Graphitic N	Oxidized N
c-FePc	2.82	0.21	0.13	0.56	1.33	0.59
c-(FePc+Pc)	3.06	0.30	0.17	0.57	1.50	0.52
c-(FePc+Pc+ZnCl₂)	3.14	0.37	0.25	0.61	1.68	0.23

Fig. 4. 57Fe Mo?ssbauer spectra of c-FePc (a) and c-(FePc+Pc+ZnCl2) (b) catalysts.

Table 2 Mo?ssbauer parameters for the fitted components and their assignments for c-FePc and c-(FePc+Pc+ZnCl2).

Catalyst	Component	IS (mm s^-1)	QS (mm s^-1)	HF (T)	Real Area (%)	Assignment
c-FePc	Singlet 1	0.05	—	—	8.7	γ-Fe
	Doublet 1	0.26	3.52	—	2.6	Fe^IIN₄/C, medium spin
	Doublet 2	0.51	0.43	—	3.3	Fe^IIN₄/C, low spin
	Sextet 1	0.46	-0.12	49.692	9.3	Fe₃O₄
	Sextet 2	0.59	-0.32	45.319	2.3	Fe₃O₄
	Sextet 3	0.13	-0.05	33.061	7.0	α-Fe
	Sextet 4	0.34	-0.02	20.414	66.8	Fe₃C
c-(FePc+Pc+ZnCl₂)	Doublet 1	0.42	3.32	—	32.9	Fe^IIN₄/C, medium spin
	Doublet 2	0.35	0.89	—	52.3	Fe^IIN₄/C, low spin
	Doublet 3	0.52	1.93	—	14.9	Fe^IIN₂₊₂/C, high spin

Fig. 5. CV curves (a), ORR polarization curves (b) and half-wave potential (E1/2) and kinetic current density (jk) (c) at 0.9 V (vs. RHE) for c-FePc, c-(FePc+Pc), c-(FePc+Pc+ZnCl2) and Pt/C. Electron transfer number (n) and H2O2 yield (d), methanol tolerance (e) and durability test (f) at 0.70 V (vs. RHE) for c-(FePc+Pc+ZnCl2) and 20 wt% Pt/C.

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Synergy of staggered stacking confinement and microporous defect fixation for high-density atomic Fe^II-N₄ oxygen reduction active sites

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