Electrochemical Study of Hydrogen Adsorption/Reduction (HAR) Reaction on Graphene Oxide as Electrocatalyst for Proton Exchange Membrane Fuel Cells

Document Type : Research Paper


1 AmirKabir university of Technology

2 AmirKabir University of Technology


In the current work, graphene oxide (GO) samples were prepared at room temperature from graphite flakes using a modified Hummer's method to produce metal-free electrocatalysts. The effect of the duration of the oxidation process on the structural, chemical and physical characteristics of the GO samples was evaluated using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), ion-exchange capacity (IEC) measurements and Field-emission scanning electron microscopy (FESEM). Electrochemical behavior of the GO samples towards hydrogen adsorption/reduction (HAR) reactions was evaluated using a typical three-electrode electrochemical cell at room temperature under N2 atmosphere. Increasing the oxidation time from 3 h to 5 h resulted in dramatic decreases in the number of epoxy and carboxyl groups, interlayer spacing (~ 9.5%) and also in the IEC (~ 1.8 times) of the GO samples. Moreover, increasing the oxidation time resulted in a remarkable increase in the size of the GO sheets along two dimensions (~ 1.5 times) and also in electrochemical surface area (ECSA) of GO (~60%). CV studies revealed that increasing the oxidation time results in an increase in the current response of GO samples towards HAR reaction, indicating an enhancement in the electrochemical activity of GO. This was attributed to the formation of larger GO samples with improved electronic network.


Main Subjects

1. He D., Kou Z., Xiong Y., Cheng K., Chen X., Pan M., Mu S., "Simultaneous sulfonation and reduction of graphene oxide as highly efficient supports for metal nanocatalysts", Carbon, 2014,66:312.
2. Woo S., Lee J., Park S.K., Kim H., Chung T.D., Piao Y., "Enhanced electrocatalysis of PtRu onto graphene separated by Vulcan carbon spacer", J. Power Sources, 2013,222:261.
3. Hsieh C.T., Liu Y.Y., Roy A.K., "Pulse electrodeposited Pdnanoclusters on graphene-based electrodes for proton exchange membrane fuel cells", Electrochimica Acta, 2012,64:205.
4. Zhang X., Sui Z., Xu B., Yue S., Luo Y., Zhan W.,"Mechanically strong and highly conductive graphene aerogel and its use as electrodes for electrochemical power sources", J. Mater. Chem., 2011,21:6494.
5. Fang Z., Liu Z., Wang Y., Ajayan P.M., Nordlander P., Halas N.J.,"Graphene-antenna sandwich photodetector", Nano Lett., 2012,12:3808.
6. Wolf E. L., Applications of Graphene - An Overview, Springer, 2014.
7. Boukhvalov D.W., Dreyer D.R., Bielawski C.W., Son Y.W., "A Computational Investigation of the Catalytic Properties of Graphene Oxide: Exploring Mechanisms by using DFT Methods", ChemCatChem, 2012,4:1844.
8. Jung J.H., Park H.J., Kim J., Hur S.H., "Highly durable Pt/graphene oxide and Pt/C hybrid catalyst for polymer electrolyte membrane fuel cell", J. Power Sources, 2014,248:1156.
9. Tiido K., Alexeyeva N., Couillard M., Bock C., MacDougall B., Tammeveski K., "Graphene-TiO2 Composite Supported Pt Electrocatalyst for Oxygen Reduction Reaction", J. Electrochimica Acta, 2013,107:509.
10. Su C., Acik M., Takai K., Lu J., Hao S.J., Zheng Y., Wu P., Bao Q., Enoki T., Chabal Y.J., Loh K.P., "Probing the catalytic activity of porous graphene oxide and the origin of this behaviour", Nat. Commun., 2012,3:1298.
11. Yuan L., Jiang L., Liu J., Xia Z., Wang S., Sun G., "Facile synthesis of silver nanoparticles supported on three dimensional graphene oxide/carbon black composite and its application for oxygen reduction reaction", Electrochimica Acta, 2014,135:168.
12. Zheng Y., Jiao1 Y., Zhu Y., Li L.H., Han Y., Chen Y.,Du A., Jaroniec M., Qiao S.Z., "Hydrogen evolution by a metal-free electrocatalyst", Nat.Commun., 2014,5:3783.
13. Moaven Sh., Naji L., Afshar Taromi F., Sharif F., "Photovoltaic Performance of Flexible Graphene/Ag Nanocomposite Electrode-Based Polymer Solar Cells under Bending", RSC Advances, 2015,5:30889.
14. Hammond C., The Basics of Crystallography and Diffraction, Oxford University Press, 2015.
15. Warren B. E., X-ray Diffraction, Courier Corporation, 1969.
16. Zeng C., Tang Z., Guo B., Zhang L.,"Supramolecular ionic liquid based on graphene oxide", Phys. Chem. Chem. Phys., 2012,28:9838.
17. Shen J., Yan B., Shi M., Ma H., Lia N., Ye M.,"One step hydrothermal synthesis of TiO2-reduced graphene oxide sheets", J. Mater. Chem., 2011,10:3415.
18. Stobinski L., Lesiak B., Malolepszy A., Mazurkiewicz M., Mierzwa B., Zemek J., Jiricek P., Bieloshapka I.,"Graphene oxide and reduced graphene oxide studied by the XRD, TEM and electron spectroscopy methods", J. Electron Spectrosc., 2014,195:145.
19. Lerf A., He H., Forster M., Klinowski J., "Structure of Graphite Oxide Revisited", J. Phys. Chem. B,1998,102, 4477.
20. Gao W., Graphene Oxide: Reduction Recipes, Spectroscopy, and Applications, Springer, 2015.
21. Liang H.W., Cao X., Zhou F., Cui C.H., Zhang W.J., Yu S.H.,"A free-standing Pt-nanowire membrane as a highly stable electrocatalyst for the oxygen reduction reaction", Adv. Mater., 2011,23:1467.
22. Matsumoto Y., Tateishi H., Koinuma M., Kamei Y., Ogata C., Gezuhara K., Hatakeyama K., Hayami S., Taniguchi T., Funatsu A.,"Electrolytic graphene oxide and its electrochemical properties", J. Electroanal. Chem., 2013,704:233.