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. 2023 Mar 30;13(7):1233.
doi: 10.3390/nano13071233.

Nitrogen-Doped Graphene Oxide as Efficient Metal-Free Electrocatalyst in PEM Fuel Cells

Adriana Marinoiu  1 , Mircea Raceanu  1   2 , Elena Carcadea  1 , Mihai Varlam  1
Affiliations

Nitrogen-Doped Graphene Oxide as Efficient Metal-Free Electrocatalyst in PEM Fuel Cells

Adriana Marinoiu et al. Nanomaterials (Basel). .

Abstract

Nitrogen-doped graphene is currently recognized as one of the most promising catalysts for the oxygen reduction reaction (ORR). It has been demonstrated to act as a metal-free electrode with good electrocatalytic activity and long-term operation stability, excellent for the ORR in proton exchange membrane fuel cells (PEMFCs). As a consequence, intensive research has been dedicated to the investigation of this catalyst through varying the methodologies for the synthesis, characterization, and technologies improvement. A simple, scalable, single-step synthesis method for nitrogen-doped graphene oxide preparation was adopted in this paper. The physical and chemical properties of various materials obtained from different precursors have been evaluated and compared, leading to the conclusion that ammonia allows for a higher resulting nitrogen concentration, due to its high vapor pressure, which facilitates the functionalization reaction of graphene oxide. Electrochemical measurements indicated that the presence of nitrogen-doped oxide can effectively enhance the electrocatalytic activity and stability for ORR, making it a viable candidate for practical application as a PEMFC cathode electrode.

Keywords: electrocatalyst; long-term operation stability; metal-free; nitrogen-doped graphene oxide; oxygen reduction reaction; proton-exchange membrane fuel cells.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
(a) SEM images of graphene oxide (GO); (b) SEM images of nitrogen-doped graphene oxide materials prepared by using different nitrogen precursors: N/GO_A (left)—from ammonia; N/GO_U (middle)—from urea, and N/GO_N (right)—from nitric acid.
Figure 2
Figure 2
FT−IR spectra of: (a) GO and (b) Nitrogen-doped graphene oxide materials prepared by using different nitrogen precursors: N/GO_A from ammonia; N/GO_U from urea, and N/GO_N from nitric acid.
Figure 3
Figure 3
XPS high resolution spectra for non-doped graphene oxide (GO); (a) Carbon (C1s); (b) Oxygen (O1s).
Figure 4
Figure 4
XPS high resolution spectra for nitrogen-doped graphene oxide synthesized using ammonia (N/GO_A); (a) Carbon (C1s); (b) Oxygen (O1s); (c) Nitrogen N1s.
Figure 5
Figure 5
XPS high resolution spectra for nitrogen-doped graphene oxide synthesized using urea (N/GO_U); (a) Carbon (C1s); (b) Oxygen (O1s); (c) Nitrogen N1s.
Figure 6
Figure 6
XPS high resolution spectra for nitrogen-doped graphene oxide synthesized using nitric acid (N/GO_N); (a) Carbon (C1s); (b) Oxygen (O1s); (c) Nitrogen N1s.
Figure 6
Figure 6
XPS high resolution spectra for nitrogen-doped graphene oxide synthesized using nitric acid (N/GO_N); (a) Carbon (C1s); (b) Oxygen (O1s); (c) Nitrogen N1s.
Figure 7
Figure 7
(a) N2 adsorption–desorption isotherms; and (b) BJH curves corresponding to N/GO_A.
Figure 8
Figure 8
(a) N2 adsorption–desorption isotherms and (b) BJH curves corresponding to N/GO_U.
Figure 9
Figure 9
(a) N2 adsorption–desorption isotherms and (b) BJH curves corresponding to N/GO_N.
Figure 10
Figure 10
Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) measurements of nitrogen-doped graphene oxides. (a) TGA and DSC curves corresponding to N/GO_A. (b) TGA and DSC curves corresponding to N/GO_U. (c) TGA and DSC curves corresponding to N/GO_N.
Figure 10
Figure 10
Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) measurements of nitrogen-doped graphene oxides. (a) TGA and DSC curves corresponding to N/GO_A. (b) TGA and DSC curves corresponding to N/GO_U. (c) TGA and DSC curves corresponding to N/GO_N.
Figure 11
Figure 11
Cyclic voltamograms at different scan rates for N/GO_A (a) and N/GO_U (b) for BoL. Right bottom insert plot of the dependency of oxidation peak current on the square root of the rate.
Figure 12
Figure 12
Chronoamperometric curves of different catalysts synthesized in the present work in 0.1 M KOH electrolyte at a constant potential of 0.3 V for 1000 min.
Figure 13
Figure 13
Cyclic voltamograms at different scan rates for N/GO_A (a) and N/GO_U (b) for EoL. Right bottom insert plot of the dependency of the oxidation peak current on the square root of rate.
Figure 14
Figure 14
Nyquist plots of the catalysts N/GO_A (a) and N/GO_U (b).
Figure 15
Figure 15
PEMFC performance using N/GO_A -based MEA. (a) Polarization and power density curves; (b) current variation profile depending on voltage; (c) flow rates consumed; (d) profiles: temperature of the PEMFC with MEA based on nitrogen doped graphene, and dew points of the reactants.
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