Iron Phthalocyanine Coated Nitrogen-doped Hollow Carbon Spheres for Efficient Catalysis of Oxygen Reduction Reaction

doi:10.7503/cjcu20220677

Abstract

Abstract:

It is imperative to develop low-cost and high-performance catalysts for oxygen reduction reaction（ORR）. Although iron phthalocyanine（FePc） has been proved as an efficient catalyst for ORR decades ago， it cannot replace commercial Pt/C due to its poor electronic conductivity and unsatisfied stability. Considering the chemical stability， high electronic conductivity， and intrinsic catalytic activity of nitrogen-doped carbons， herein， FePc coated nitrogen-doped hollow carbon（FePc-NHC） has been fabricated by carbonization of polystyrene@polydopamine spherical precursors， followed by the loading of FePc. A series of hollow spherical FePc-NHCS samples was prepared by adjusting the pyrolysis temperature and loading amount of FePc. Benefiting from the hierarchical porous structure， high specific surface area， proper nitrogen doping， and FePc loading， the optimized FePc-NHCS displayed an excellent catalytic activity for ORR in alkaline electrolyte， with a remarkable long-term stability and a high half-wave potential of 0.862 V（vs. RHE）， outperforming Pt/C（0.848 V）. This work proved that hybridization is an effective pathway to strength the positive properties of each component. Also， structural and compositional modification is efficient to optimize the ORR performance of a catalyst.

Key words: Hard-template method, Non-noble metal catalyst, Hollow carbon sphere, Oxygen reduction reaction

CLC Number:

O643

TrendMD:

LI Ziruo, ZHANG Hongjuan, ZHU Guoxun, XIA Wei, TANG Jing. Iron Phthalocyanine Coated Nitrogen-doped Hollow Carbon Spheres for Efficient Catalysis of Oxygen Reduction Reaction[J]. Chem. J. Chinese Universities, 2023, 44(1): 20220677.

Figures/Tables 6

Fig.1 SEM images of PS(A), PS@PDA(B), NHCS(C), and FePc⁃NHCS(D), XRD patterns of PS, PDA, PS@PDA, NHCS and FePc⁃NHCS(E) and TG curves of PS, PDA and PS@PDA measured under N2 atmosphere(F)

Fig.2 SEM images(A1―A3), XRD patterns(B), high resolution N1s XPS spectra(C), Raman spectra(D), N2 adsorption⁃desorption isotherms(E) and pore size distributions(inset) of NHCS⁃x(x=900, 1000, 1100)（A1) NHCS⁃900; (A2) NHCS⁃1000; (A3) NHCS⁃1100.

Fig.3 SEM images(A1―A3), XRD patterns(B), high resolution N1s (C) and Fe2p XPS spectra(D) of FePc⁃NHCS⁃x(x=900, 1000, 1100), and LSV of NCS⁃1000, FePc⁃NCS⁃1000, NHCS⁃x, FePc⁃NHCS⁃x(x=900, 1000, 1100), and Pt/C(20%) at 1600 r/min with a scan rate of 10 mV/s(E)(A1) FePc⁃NHCS⁃900; (A2) FePc⁃NHCS⁃1000; (A3) FePc⁃NHCS⁃1100.

Table 1 Elemental content(%, atom fraction) in FePc-NHCS-x(x=900, 1000, 1100)

Sample	C	N	O	Fe
FePc⁃NHCS⁃900	83.01	6.63	10.12	0.24
FePc⁃NHCS⁃1000	85.30	4.33	9.93	0.44
FePc⁃NHCS⁃1100	87.39	3.50	8.77	0.34

Fig.4 SEM images of FePc⁃NHCS⁃1000⁃y(y=1, 2, 3 from left to right)(A), TEM(B), STEM(C1) and elemental mapping(C2—C4) images of FePc⁃NHCS⁃1000⁃2, and XRD patterns(D) and high resolution N1s XPS spectra(E) of FePc⁃NHCS⁃1000⁃y(y=1, 2, 3)

Fig.5 LSV of FePc⁃NHCS⁃1000⁃y(y=1, 2, 3) and Pt/C(20%) at 1600 r/min with a scan rate of 10 mV/s(A), different rotation speeds(B), and RRDE curves(C) of FePc⁃NHCS⁃1000⁃2 in O2⁃saturated 1 mol/L KOH with a scan rate of 10 mV/s, electron transfer number and peroxide yield of FePc⁃NHCS⁃1000⁃2 calculated from (C)(D)

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