Rapid room-temperature synthesis of nanocrystalline spinels as oxygen reduction and evolution electrocatalysts

Journal name:
Nature Chemistry
Volume:
3,
Pages:
79–84
Year published:
DOI:
doi:10.1038/nchem.931
Received
Accepted
Published online

Abstract

Spinels can serve as alternative low-cost bifunctional electrocatalysts for oxygen reduction/evolution reactions (ORR/OER), which are the key barriers in various electrochemical devices such as metal–air batteries, fuel cells and electrolysers. However, conventional ceramic synthesis of crystalline spinels requires an elevated temperature, complicated procedures and prolonged heating time, and the resulting product exhibits limited electrocatalytic performance. It has been challenging to develop energy-saving, facile and rapid synthetic methodologies for highly active spinels. In this Article, we report the synthesis of nanocrystalline MxMn3–xO4 (M = divalent metals) spinels under ambient conditions and their electrocatalytic application. We show rapid and selective formation of tetragonal or cubic MxMn3–xO4 from the reduction of amorphous MnO2 in aqueous M2+ solution. The prepared CoxMn3–xO4 nanoparticles manifest considerable catalytic activity towards the ORR/OER as a result of their high surface areas and abundant defects. The newly discovered phase-dependent electrocatalytic ORR/OER characteristics of Co–Mn–O spinels are also interpreted by experiment and first-principle theoretical studies.

At a glance

Figures

  1. Structural analysis of the synthesized nanocrystalline spinels.
    Figure 1: Structural analysis of the synthesized nanocrystalline spinels.

    a,b, Rietveld refined XRD patterns of CoMnO–B (a) and CoMnO–P (b) with experimental data (red dots), calculated profiles (black line), allowed Bragg diffraction positions (vertical bars) and difference curve (blue line). c,d, Schematic representation of tetragonal (c) and cubic (d) spinels.

  2. Characterization of CoMnO-B and CoMnO–P.
    Figure 2: Characterization of CoMnO-B and CoMnO–P.

    a,b, SEM images showing the porous nanostructures of CoMnO–B (a) and the nanoparticulate morphology of CoMnO–P (b). c,d, High-resolution TEM images and the corresponding FFT patterns (inset), showing the single tetragonal spinel phase (c) and the double phases of cubic spinel and monoclinic birnessite (d). e,f, EDS spectra confirming the elemental ratio of cobalt to manganese.

  3. Electrochemical application of nanocrystalline CoMnO–B and CoMnO–P as ORR and OER electrocatalysts.
    Figure 3: Electrochemical application of nanocrystalline CoMnO–B and CoMnO–P as ORR and OER electrocatalysts.

    a, Voltammograms of the ORR using catalyst-modified RDEs in O2-saturated alkaline electrolyte. b, K–L plots for the ORR. c, Galvanostatic discharge curves of the prototype zinc–air battery made with a nanoparticle catalyst layer. d, Voltammetry curves of the OER measured at different catalyst-modified electrodes.

  4. First-principle study of surface oxygen adsorption on different sites of cubic and tetragonal spinel phases.
    Figure 4: First-principle study of surface oxygen adsorption on different sites of cubic and tetragonal spinel phases.

    ad, Geometries and binding energies of oxygen molecules (purple) on cobalt (cyan) or manganese (grey) defect sites. Red spheres represent lattice oxygen. e,f, Corresponding density of states of bare and O2-adsorbed spinels.

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Affiliations

  1. Institute of New Energy Material Chemistry, Chemistry College, Nankai University, Tianjin 300071, China

    • Fangyi Cheng,
    • Jian Shen,
    • Bo Peng,
    • Yuede Pan,
    • Zhanliang Tao &
    • Jun Chen
  2. Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Chemistry College, Nankai University, Tianjin 300071, China

    • Fangyi Cheng,
    • Zhanliang Tao &
    • Jun Chen

Contributions

F.C., J.S. and Y.P. synthesized and characterized the materials. F.C. and J.S. carried out electrochemical measurements. B.P. performed the first-principles simulation. All authors contributed to the data analysis. J.C. directed the research.

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The authors declare no competing financial interests.

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