N/S Co-doped Non-precious Metal as Non-platinum Cathode Catalyst for Alkaline Membrane Fuel Cells†

doi:10.7503/cjcu20131208

Abstract

Abstract:

N/S co-doped non-precious metal material for the oxygen reduction reaction(ORR) was prepared with ferrous sulfate heptahydrate(FeSO₄·7H₂O), pyrrole and p-toluenesulfonic acid(TsOH) as Fe, N and S precursors supported on vulcan XC 72R, and followed by heat treatment in an inert atmosphere at 600 ℃. The electrochemical techniques such as cyclic voltammetry(CV) and rotating disk electrode(RDE) were employed with the Koutechy-Levich theory to make clear the ORR kinetical constants and the reaction mechanism. It is found that the catalysts dual-doped with TsOH show significantly improved ORR activity relative to the TsOH-free one. The overall electron transfer numbers for the catalyzed ORR are determined to be 3.899 and 3.098, respectively, for the catalysts with and without TsOH-doping. And these catalysts exhibit superior methanol tolerance to commercial 40%Pt/C catalyst. The XRD results demonstrate the decomposition of the precursors because of pyrolysis and formation of Fe-N_x-C active surface groups and some less active species. XPS analysis indicate that the pyrrolic-N groups are the most active sites and sulfur species are also structurally bonded to carbon in the forms of C—S_n—C and oxidized —SO_n— bonds, which are beneficial for ORR.

Key words: Dual-doped non-precious metal catalyst, Oxygen reduction reaction, Stability, Alkaline anion exchange membrane fuel cell

CLC Number:

O643
O614

TrendMD:

XU Li, PAN Guoshun, LIANG Xiaolu, LUO Guihai, Zou Chunli, CHEN Gaopan. N/S Co-doped Non-precious Metal as Non-platinum Cathode Catalyst for Alkaline Membrane Fuel Cells^†[J]. Chem. J. Chinese Universities, 2014, 35(5): 1029.

Figures/Tables 7

Fig.1 Polarization curves(A) and CVs(B) of catalysts Fe-N/C-TsOH-600(a) and Fe-N/C-600(b) in O2-saturated 0.1 mol/L KOH solution

Fig.2 Polarization curves for ORR on Fe-N/C-600(A) and Fe-N/C-TsOH-600(B) catalyst measured in O2-saturated 0.1 mol/L KOH electrolytes at various rotation rates^ω/(r·min-1) from top to bottom: 300, 600, 900, 1200, 1500, 1800, 2100, 2400.

Fig.3 Koutecky-Levich plots for Fe-N/C-600(A) and Fe-N/C-TsOH-600(B) in O2-saturated 0.1 mol/L KOH solution at the potential of -0.6, -0.4 and -0.2 V, respectively

Fig.4 Polarization curves for the oxygen reduction in O2-saturated 0.1 mol/L KOH on Fe-N/C-TsOH-600 before and after the potential cycling stability test(A) and iloss at different potential for the ORR in O2-saturated 0.1 mol/L KOH on Fe-N/C-TsOH-600 as a function of the number of potential cycling(B)^(A) Electrode rotating rate: 1500 r/min. Potential cycling was performed in N2-saturated 0.1 mol/L KOH with a scan rate of 50 mV/s between -0.76 and 0.14 V(vs. SHE) for 0, 1500, 4800 and 6000 cycles.

Fig.5 Polarization curves for O2 reduction on Pt/C electrode(A) and Fe-N/C-TsOH-600(B) in O2-saturated 0.1 mol/L KOH electrolyte without and with different concentrations of methanol solution^Potential scan rate: 5 mV/s. Electrode rotating rate: 1500 r/min. c(CH3OH)/(mol·L-1): a. 0; b. 0.5; c. 1.0; d. 5.0.

Fig.6 XRD patterns of Fe-N/C-TsOH-600(a) and Fe-N/C-TsOH(b) catalysts^Peaks 1—5: Fe3O4(022); Fe3O4(113); Fe(011), FeC(013); Fe3O4(115) and Fe3O4(044).

Fig.7 XPS spectra of deconvoluted N1s(A, B) and S2p(C, D) for catalyst Fe-N/C-TsOH before(A, C) and after(B, D) pyrolyzed at 600 ℃

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