Se-doping strategy regulating mass transfer and electronic structure of Fe-N-C electrocatalysts for proton exchange membrane fuel cells

doi:10.1016/S1872-2067(25)64715-2

Abstract

Abstract:

The limited activity of atomically-dispersed M-N-C electrocatalysts severely restricts their applicability in the oxygen reduction reaction (ORR) for proton exchange membrane fuel cells (PEMFC). Herein, we design and synthesize Se-doped Fe-N-C hierarchical porous electrocatalyst (FeN₄/SeC₂) by optimizing carbon structure and FeN₄ coordination environment. The FeN₄/SeC₂ electrocatalyst exhibits outstanding ORR activity in 0.1 mol L^-1 HClO₄, and the resulting PEMFC presents a peak power density of 1.20 W cm^-2 in H₂-O₂ condition at a back pressure of 200 kPa, ranking in the top levels among most reported non-precious metal catalyst-based fuel cells. The lower O₂ transfer resistance of FeN₄/SeC₂-based membrane electrode assembly than FeN₄-based one means faster O₂ transport in triple-phase boundary (TPB), and Density functional theory calculation further reveals that the synergistic catalysis between porous SeC₂ and FeN₄-OH species can efficiently lower the energy barriers for the rate-determining step of the ORR. In short, the outstanding performance of FeN₄/SeC₂ in PEMFC is ascribed to the Se-doping, which introduces more defects and larger mesoporosity and therefore facilitates ionomer infiltration and O₂ transfer and charge transfer in TPB. The effective strategy of enhancing mass and charge transfers in TPB is anticipated to be applicable in the construction of highly efficient ORR electrocatalysts.

Key words: Se-doping, Synergistic catalysis, Enhancing mass transfer, Oxygen reduction, Proton exchange membrane fuel cells

Lin Xu, Li Danyang, Huang Shiqing, Sun Panpan, Huang Yan, Wang Shitao, Zheng Lirong, Cao Dapeng. Se-doping strategy regulating mass transfer and electronic structure of Fe-N-C electrocatalysts for proton exchange membrane fuel cells[J]. Chinese Journal of Catalysis, 2025, 75: 73-83.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64715-2

https://www.cjcatal.com/EN/Y2025/V75/I8/73

Figures/Tables 4

Fig. 1. (a) Synthesis scheme for FeN4/SeC2. HAADF-STEM image (b) and corresponding EDS element mapping (c) of FeN4/SeC2. (d) AC-HAADF-STEM images of FeN4/SeC2. N2 adsorption-desorption isotherms (e) and pore size distributions (f) of FeN4/SeC2 and Fe-NC. (g) Raman spectra of FeN4/SeC2, Fe-NC, Se-NC and NC.

Fig. 2. High-resolution XPS patterns of (a) Fe 2p and (b) Se 3d patterns of FeN4/SeC2/Fe-NC and FeN4/SeC2/Se-NC. (c) XANES spectra and (d) FT-EXAFS spectra of FeN4/SeC2, Fe-NC, Fe2O3 and Fe foil in Fe K-edge. (e) XANES spectra and (f) FT-EXAFS spectra of FeN4/SeC2, Se-NC, SeO2 and Se foil in Se K-edge. (g-j) Wavelet transform of the k2-weighted EXAFS data of FeN4/SeC2, Fe-NC, Fe2O3 and Fe foil.

Fig. 3. LSV curves (a) and Tafel plots (b) of FeN4/SeC2, Fe-NC, Se-NC, NC and Pt/C in O2-saturated 0.1 mol L-1 HClO4. Polarization and power density curves for H2-O2 PEMFC. Test conditions: 3.0 mg cm-2 for cathodic catalysts (FeN4/SeC2/Fe-NC), 0.2 mg cm-2 for anodic catalyst (40% Pt/C), GORE-12μm membrane, 5 cm2 electrode area, 80 °C, 100% relative humidity, 200 kPa (c) and 100 kPa (d). (e) H2-O2 PEMFC stability measurement at a constant voltage of 0.67 V for FeN4/SeC2-based MEA and Fe-NC-based MEA. (f) Polarization and power density curves for H2-Air PEMFC. Test conditions same as H2-O2 condition. (g) Relationship between Rtotal and absolute gas pressure. Insets are Rnp and Rp. (h) An Arrhenius plots. The relationship between exchange current density (i0) and k0 is k0 = i0/n*F*C, so log(i0) - 1000/T fitting (Ink0 = -Ea/RT + InA), the slope is -Ea/RT, and the activation energy Ea of electron transfer can be obtained. (i) Nyquist plots recorded at 1.0 A cm-2 of FeN4/SeC2 and Fe-NC, the inset shows the equivalent circuit model, Rct and Rmt obtained by EIS fitting.

Fig. 4. (a) Geometric structures of the FeN4/SeC2 and FeN4-edge. (b) Surface Pourbaix diagrams under ORR working conditions of the FeN4/SeC2, where the dash line represents the limiting potential (UL) of corresponding catalyst. (c) Gibbs free-energy diagrams at 0 V on FeN4/SeC2-OH and FeN4-edge-OH. (d) The PDOS diagram of Fe 3d orbitals on FeN4/SeC2-OH and FeN4-edge-OH.

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