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SCIENCE CHINA Chemistry
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SCIENCE CHINA Chemistry, Volume 62 , Issue 4 : 417-429(2019) https://doi.org/10.1007/s11426-018-9441-4

Metal-organic framework based nanomaterials for electrocatalytic oxygen redox reaction

Kexin Zhang , Wenhan Guo , Zibin Liang , Ruqiang Zou *
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  • ReceivedDec 31, 2018
  • AcceptedFeb 12, 2019
  • PublishedMar 4, 2019
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Abstract


Funded by

the National Natural Science Foundation of China(51825201)

the National Key Research and Development Program of China(2017YFA0206701)

the National Program for Support of Top-notch Young Professionals

and Changjiang Scholar Program.


Acknowledgment

This work was supported by the National Natural Science Foundation of China (51825201), the National Key Research and Development Program of China (2017YFA0206701), the National Program for Support of Top-notch Young Professionals, and Changjiang Scholar Program.


Interest statement

The authors declare that they have no conflict of interest.


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  • Click to view Download high-quality image

    Figure 1

    Schematic illustration of MOFs and MOF-derived nanostructures for ORR and OER (color online).

  • Click to view Download high-quality image

    Figure 2

    Volcano plots for different electrochemical process. (a) ORR activity plotted as a function of the oxygen binding energy. Reprinted with permission from Ref. [23]. Copyright 2004 American Chemical Society. (b) Activity trends for OER as a function of ΔGO*−ΔGOH* for Co3O4, MnxOy, rutile, and anatase. Reprinted with permission from Ref. [24]. Copyright 2011 John Wiley and Sons.

  • Click to view Download high-quality image

    Figure 3

    (A) Crystal structure of NPC-4. (B) Schematics for O2 reduction catalyzed by as-prepared NPC-4 and activated NPC-4. (C) CV curve a, b, c of RGO, activated NPC-4 modified RGO/GCE in N2-saturated PBS solution, activated NPC-4 modified RGO/GCE in O2-saturated PBS solution, respectively. Reprinted with permission from Ref. [32]. Copyright 2014 Royal Society of Chemistry (color online).

  • Click to view Download high-quality image

    Figure 4

    Optimized structures for the stable adsorbed O2 on (a) N-doped nanocarbon, (b) N,S-isolated nanocarbon, and (c) N,S-coupled nanocarbon. Free-energy diagram of ORR on (d) N-doped nanocarbon, (e) N,S-isolated nanocarbon, and (f) N,S-coupled nanocarbon in alkaline media. Reprinted with permission from Ref. [39]. Copyright 2017 Royal Society of Chemistry (color online).

  • Click to view Download high-quality image

    Figure 5

    (a) Aberration-corrected HAADF-STEM image of Co–N–C-10. (b) Magnified image marked in (a). (c) ORR polarization curves for Co–N–C-x, N–C and commercial Pt/C catalysts in O2-saturated 0.1 M HClO4. (d) Comparison of mass-specific activity of each active site structure. Reprinted with permission from Ref. [64]. Copyright 2018 Elsevier (color online).

  • Click to view Download high-quality image

    Figure 6

    (a) Schematic illustration of the host-guest chemistry strategy. (b) Optimized structures of (i) O2, (ii) OOH, (iii) O, and (iv) OH adsorbed on N–Fe–N4. (c) Free-energy diagrams of the reduction of O2 to H2O on the N–Fe–N4, Fe–N4, and Fe–N2 structures in acid media. Reprinted with permission from Ref. [66]. Copyright 2017 American Chemical Society (color online).

  • Click to view Download high-quality image

    Figure 7

    (a) Schematic illustration of atomically dispersed MnN4 site catalyst synthesis. (b) Aberration-corrected MAADF-STEM image. (c) EEL point spectrum from the atomic site circled in red in (b). (d) Comparison of the catalytic activity of Fe–, Co– and Mn–N–C catalysts prepared from identical procedure. Reprinted with permission from Ref. [70]. Copyright 2018 Springer Nature (color online).

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    Figure 8

    (a) SEM image, (b) AFM image of NiFe-UMNs. (c) LSV curves of NiFe-UMNs, CoFe-UMNs, bulk NiFe-MOFs, commercial RuO2 and IrO2 in O2-saturated 1 M KOH. (d) Chronoamperometric curves for long term stability tests of NiFe-UMNs at the constant overpotential of 0.28 V and the inset is the comparison with commercial RuO2 (red curve). Reprinted with permission from Ref. [72]. Copyright 2018 Elsevier (color online).

  • Click to view Download high-quality image

    Figure 9

    (a) Schematic illustration for the fabrication of Ni-Co@NiCoO2/C PMRAs. (b) SEM image, (c) HRTEM image of a typical NiCo@NiCoO2 core-shell nanoparticle. (d) High resolution XPS spectra ofO 1s of NiCo@NiCoO2/C PMRA. Reprinted with permission from Ref. [83]. Copyright 2018 John Wiley and Sons (color online).

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    Figure 10

    (a) Schematic illustration of the formation process of NiCoP/C nanoboxes. (b) FESEM image, (c) TEM image of NiCoP/C nanoboxes. (d) OER polarization curves of Ni–Co LDH, NiCoP, and NiCoP/C nanoboxes in an O2-saturated 1.0 M KOH. Reprinted with permission from Ref. [94]. Copyright 2017 John Wiley and Sons (color online).

  • Table 1   Summary of ORR performance of MOF-based catalysts

    Catalyst

    Active sites

    Eonset (V)

    E1/2 (V)

    Ref.

    NPC-1000

    Doped-N

    1.020

    0.902

    [47]

    NGPC-1000-10

    Doped-N

    0.947

    0.767

    [37]

    N,S-NH3-C-7

    Doped-N, S

    –

    0.837

    [39]

    MIL-88B-NH3

    Fe/FeC3

    1.030

    0.920

    [97]

    Co@Co3O4@C-CM

    Co/Co3O4

    0.930

    0.810

    [98]

    LDH@ZIF-67-800

    Co–N

    0.940

    0.830

    [99]

    H-CoNC

    Co–Nx

    0.872

    0.796

    [53]

    Co@NC-MOF-2-900

    CoNx–Cy

    and CoNx

    0.930

    0.820

    [63]

    20Co-NC-1100

    Co–N4

    0.930

    0.800

    [69]

    C-Fe-Z8-Ar

    Fe–N4

    0.950

    0.820

    [65]

    Fe-ZIF-50 nm

    Fe–N4

    –

    0.850

    [68]

  • Table 2   Summary of OER performance of MOF-based catalysts

    Catalyst

    Active sites

    η@10 mA cm−2 (mV)

    Tafel slope (mV dec−1)

    Ref.

    FeNi@NCNT

    FeNi alloy

    300

    48

    [77]

    2D Co3O4/CBDC

    Co3O4

    208

    50

    [81]

    CoMo–H

    CoO-MoO2

    312

    69

    [85]

    NF@NC-CoFe2O4/C NRAs

    CoFe2O4

    240

    45

    [82]

    Co9S8/NSCNFs-850

    Co9S8

    302

    54

    [86]

    CoSe2-450

    CoSe2

    330

    79

    [88]

    CoTe2@NCNTFs

    CoTe2

    330

    83

    [91]

    CoP/rGO-400

    CoP

    340

    66

    [100]

    NiCoP/C nanoboxes

    NiCoP

    330

    96

    [94]

    H3LCoCN800

    Co2P2O7

    320

    64

    [96]