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Controllable Fabrication of Co3−xMnxO4 with Tunable External Co3+/Co2+ Ratio for Promoted Oxygen Reduction Reaction

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Abstract

Co3−xMnxO4 is a bimetal oxide with excellent electrochemical activity in alkaline solution, has been regarded as a promising alternative in the field of ion-air batteries and proton exchange membrane fuel cell (PEMFC). Herein, we report a simple solvothermal-calcination method to fabricate Co3−xMnxO4 with tunable external Co3+/Co2+ and Mn3+/Mn2+ ratio. The tunable ratio of element valence in the bimetal results in a higher exposure of active center for oxygen redox reaction (ORR), and thus lead to a better ORR activity, which was confirmed by X-ray photoelectron spectroscopy characterizations and electrochemical measurements. Specially, Co1.8Mn1.2O4 with a Co3+/Co2+ ratio of 2.08 showed an overpotential of 0.37 V at benchmark ORR current density of 3 mA/cm2 in 0.1 M KOH, which is lower than that of pure oxide (Mn3O4 0.53 V and Co3O4 0.56 V). In addition, the as prepared Co1.8Mn1.2O4 exhibited a positive half-wave potential (0.83 V vs RHE) due to their more active sites, promotes charge transfer, adsorption and desorption of oxygen species. This work provides a strategy for the design and fabrication of earth-abundant, low-cost electrocatalysts for PEMFC in practical applications.

Graphic Abstract

Co3−xMnxO4 was fabricated by tuning external Co3+/Co2+ and Mn3+/Mn2+ ratio, and the activity initially shows a positive correlation with the ration of Co3+/Co2+ in Co3−xMnxO4.

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Acknowledgements

This research was funded by the National Natural Science Foundation of China (No. 21808172), Tianjin Municipal Natural Science Foundation (Nos. 18JCQNJC05800, 18JCZDJC37200), Innovation Fund for Young Talents of TUST and the Fund of Tianjin Key Laboratory of Brine Chemical Engineering and Resource Eco-utilization (No. BCERE201909), Yangtze Scholars and Innovative Research Team in University (IRT-17R81), Innovative Research Team of Tianjin Municipral Education Commission (TD13-5008).

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Author notes

  1. Nannan Zhao and Songbo Wang contributed equally to this work.

Authors and Affiliations

  1. College of Chemical Engineering and Materials Science, Tianjin University of Science & Technology, Tianjin, 300457, China

    Nannan Zhao, Songbo Wang, Penggao Cheng, Jianping Zhang, Lei Zhang, Wei Du & Na Tang

  2. Tianjin Key Laboratory of Brine Chemical Engineering and Resource Eco-Utilization, Tianjin University of Science & Technology, Tianjin, 300457, China

    Nannan Zhao, Songbo Wang, Penggao Cheng, Jianping Zhang, Lei Zhang, Wei Du & Na Tang

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  1. Nannan Zhao
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  2. Songbo Wang
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Correspondence to Na Tang.

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10562_2020_3381_MOESM1_ESM.docx

Schematic patterns (Fig. S1), FT-IR images (Fig. S2), SEM images (Fig. S3), XRD patterns (Fig. S4), BET curves (Fig. S5), Full XPS spectrum (Fig. S6 and S7), polarization curves (Fig. S8, S9 and S10), Comparisons of electrocatalytic activity (Table S1), Recent research (Table S2), BET data (Table S3), XPS data (Table S4, S5 and S7). (DOCX 2480 kb)

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Zhao, N., Wang, S., Cheng, P. et al. Controllable Fabrication of Co3−xMnxO4 with Tunable External Co3+/Co2+ Ratio for Promoted Oxygen Reduction Reaction. Catal Lett 151, 1810–1820 (2021). https://doi.org/10.1007/s10562-020-03381-y

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  • DOI: https://doi.org/10.1007/s10562-020-03381-y

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