Mn-doped perovskite-type oxide LaFeO<sub>3</sub> as highly active and durable bifunctional electrocatalysts for oxygen electrode reactions

doi:10.1007/s11706-020-0513-9

Front. Mater. Sci.

2020, Vol. 14

Issue (4) : 459-468 https://doi.org/10.1007/s11706-020-0513-9

RESEARCH ARTICLE

Mn-doped perovskite-type oxide LaFeO₃ as highly active and durable bifunctional electrocatalysts for oxygen electrode reactions

Jingze ZHANG¹, Sheng ZHU^1,², Yulin MIN^1,², Qunjie XU^1,²(

)

¹. Shanghai Key Laboratory of Materials Protection and Advanced Materials in Electric Power, Shanghai Engineering Research Center of Energy-Saving in Heat Exchange Systems, Shanghai University of Electric Power, Shanghai 200090, China
². Shanghai Institute of Pollution Control and Ecological Security, Shanghai 200092, China

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Abstract

Perovskite oxides based on the alkaline earth metal lanthanum for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in alkaline electrolytes are promising catalysts, but their catalytic activity and stability remain unsatisfactory. Here, we synthesized a series of LaFe₁₋_xMn_xO₃ (x = 0, 0.1, 0.3, 0.5, 0.7, 0.9 and 1) perovskite oxides by doping Mn into LaFeO₃ (LF). The results show that the doping amount of Mn has a significant effect on the catalytic performance. When x = 0.5, the catalyst LaFe_0.5Mn_0.5O₃ (LFM) exhibits the best performance. The limiting current density in 0.1 mol·L⁻¹ KOH solution is 7 mA·cm⁻², much larger than that of the commercial Pt/C catalyst (5.5 mA·cm⁻²). Meanwhile, the performance of the doped catalyst is also superior to that of commercial Pt/C in terms of the long-term durability. The excellent catalytic performance of LFM may be ascribed to its abundant O²⁻/O⁻ species and low charge transfer resistance after doping the Mn element.

Keywords oxygen electrode reaction oxygen reduction reaction oxygen evolution reaction perovskite electrocatalyst LaFeO₃

Corresponding Author(s): Qunjie XU

Online First Date: 28 September 2020 Issue Date: 09 December 2020

Cite this article:

Jingze ZHANG,Sheng ZHU,Yulin MIN, et al. Mn-doped perovskite-type oxide LaFeO₃ as highly active and durable bifunctional electrocatalysts for oxygen electrode reactions[J]. Front. Mater. Sci., 2020, 14(4): 459-468.

URL:

https://academic.hep.com.cn/foms/EN/10.1007/s11706-020-0513-9
https://academic.hep.com.cn/foms/EN/Y2020/V14/I4/459

Fig.1 (a) Schematic of the LFM perovskite crystal structure. (b) XRD patterns of LF and LFM. (c) SEM image of LFM. (d) N₂ adsorption–desorption isotherm and corresponding pore size distribution (inset) of the catalyst LFM.

Fig.2 (a) TEM image and (b) HRTEM image of the perovskite catalyst LFM. (c)(d)(e)(f)(g) Element mappings of the perovskite LFM by EDS from TEM analysis.

Fig.3 XPS results of the catalyst LFM: (a) overall spectrum, and high resolution curves of (b) O 1s region, (c) Fe 2p region and (d) Mn 2p region.

Fig.4 (a) ORR LSV curves of Pt/C and LaMn_xFe₁₋_xO₃. (b) Tafel plots of Pt/C, LF and LFM catalysts. (c) LSV curves of LFM at different rotation speeds (inset figure shows the K–L plots). (d) Electrochemical stability test.

Fig.5 (a) LSV curves of LaFe₁₋_xMn_xO₃ catalysts for OER on the RDE in Ar-saturated 0.1 mol·L⁻¹ KOH solutions at 1600 r·min⁻¹ (scan rate: 10 mV·s⁻¹). (b) Tafel plots of LF, LFM and Pt/C (20%). (c) Electrochemical impedance spectra of LF and LFM catalysts. (d) LSV curves of the LFM catalyst before and after 1000 cycles in O₂-saturated 0.1 mol·L⁻¹ KOH solution.

Fig. S1 Scheme of the synthesis of

LaFe 1 − x Mn x O 3

samples.

Fig. S2XPS analysis of the LF perovskite catalyst: (a)Fe 2p region; (b)O 1s region.

Table S1 ICP data of the LFM catalyst

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