SCIENCE CHINA Chemistry, Volume 63 , Issue 10 : 1469-1476(2020) https://doi.org/10.1007/s11426-020-9795-x

Promoting selective electroreduction of nitrates to ammonia over electron-deficient Co modulated by rectifying Schottky contacts

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  • ReceivedFeb 28, 2020
  • AcceptedJun 17, 2020
  • PublishedJul 27, 2020



the National Natural Science Foundation of China(21871206,21701122)


This work was supported by the National Natural Science Foundation of China (21871206, 21701122).

Interest statement

The authors declare no conflict of interest.

Contributions statement

These authors contributed equally to this work.

Supplementary data

Supporting information

The supporting information is available online at http://chem.scichina.com and http://link.springer.com/journal/11426. The supporting materials are published as submitted, without typesetting or editing. The responsibility for scientific accuracy and content remains entirely with the authors.


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  • Scheme 1

    The schematic illustration for nitrate electroreduction to ammonia over Co/CoO NSAs (color online).

  • Figure 1

    (a) Schematic illustration for the preparation of Co/CoO NSAs on Ni foams. (b) XRD pattern of Co/CoO NSAs powders. (c) A low-magnification SEM image of Co/CoO NSAs (inset: a high-magnification SEM image of Co/CoO NSAs). (d) A TEM image of Co/CoO NSAs. (e) A HRTEM image (the red dotted areas are Co domains) of Co/CoO NSAs (color online).

  • Figure 2

    (a) UPS spectra in the cutoff energy regions of CoO NSAs (inset shows the onset energy region). (b) UPS spectra in the cutoff energy regions of Co NSAs. (c) Energy band diagrams of metal Co and p-type semiconductor CoO (EF: Fermi level; EV: valence band energy; EC: conduction band energy). (d) UPS spectra in the cutoff energy region of Co/CoO NSAs (inset shows the onset energy region). (e) The illustration of the electron transfer in the integrated Co/CoO NSAs. (f) XPS spectra of Co 2p3/2 and Co 2p1/2 in Co NSAs, Co/CoO NSAs and CoO NSAs (color online).

  • Figure 3

    (a) The LSV curves of Co/CoO NSA electrodes in 0.1 MNa2SO4 with and without NaNO3 (inset is the photograph of chromogenic results). (b) The conversion rate of nitrates and the FE of ammonia over Co/CoO NSA electrocatalysts. (c) The selectivity and the yield rate of ammonia at different potentials of Co/CoO NSAs. (d) Time-dependent concentration of nitrates and ammonia during reduction reactions over Co/CoO NSAs at −1.3 V vs. SCE (color online).

  • Figure 4

    (a) 1H NMR spectra (600 MHz) of standard samples ((15NH4)2- SO4 and (14NH4)2SO4)) and electrolytes after the NO3 reduction at −1.3 Vvs. SCE for 2 h using 14NO3 and 15NO3 as N-source. (b) Cycle-dependent conversion rates of NO3 and selectivity of ammonia over Co/CoO NSAs at −1.3 V. (c) The ammonia selectivity of Co/CoO NSAs under different nitrate concentration. (d) The conversion rates of nitrates and the FE of ammonia over different samples (color online).

  • Figure 5

    (a) DEMS measurements of electrocatalytic reduction of nitrates over Co/CoO NSAs. (b) In situ FTIR spectra of electrocatalytic reduction of nitrates over Co/CoO NSAs. (c) The diagram of free energy by DFT calculations. (d) The calculated relative reaction energy of the H2 formation on Co and Co/CoO NSAs. (e) The calculated relative reaction energy of the formation of NO, N2, N2H4 and N2O on Co and Co/CoO NSAs (color online).


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