Electrocatalysis of Pt-Based Metal Loaded TiO2 Modified Graphene Oxide for Methanol Oxidation

Main Article Content

S. Rattanakansang


Titanium dioxide (TiO2) modified graphene oxide (GO) was prepared as a support for methanol oxidation reaction. Electrodeposition of platinum (Pt) and palladium (Pd) on the obtained TiO2-GO was then carried out to study their activities on methanol oxidation. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) with energy dispersive X-ray spectroscopy (EDS) were used to identify their morphologies and chemical compositions, respectively. It was found that, TiO2 was successfully attached on GO surface and a narrow size distribution of Pt particles was found on TiO2-GO surface. EDS spectrum confirmed the presence of C, O, Ti, and Pt elements in the prepared catalysts. The electrocatalytic activities of the electrocatalysts toward oxidation of 0.5 M CH3OH in 0.5 M H2SO4 solution were examined using cyclic voltammetry (CVs). For mono-metallic Pt catalysts, the addition of TiO2 significantly enhanced methanol oxidation property and promoted CO tolerance performance. With exceptional activity and durability toward efficient methanol oxidation reaction, the forward current intensity, backward current intensity and onset potential of the 2Pt/TiO2-GO are 1.36 mA.cm-2and 0.98 mA.cm-2 and 0.44 V vs.Ag/AgCl, respectively. Long-term stabilities of theelectrocatalysts were examined by chronoamperometry (CAs). It was found that the 2Pt/TiO2-GO (0.019 mA.cm-2) showed higher current intensity than the 2Pt/GO catalyst (0.008 mA.cm-2). For bi-metallic xPt2Pd/TiO2-GO catalysts, their activities and stabilities are not outstanding but the 6Pt2Pd/TiO2-GO showed rather promising results in terms of lower potential and comparable current intensity to the 8Pt/TiO2-GO.Incorporation of Pd with Pt provided lower onset potential, lower potential at maximum current intensities (Ef) and higher stabilities compared with the catalysts without Pd.

Article Details

How to Cite
Rattanakansang, S. Electrocatalysis of Pt-Based Metal Loaded TiO2 Modified Graphene Oxide for Methanol Oxidation. Microsc. Microanal. Res. 2017, 30, 6-11.
Original Articles


1. 1 Z. Yang, J. Ren, Z. Zhang, X. Chen, G. Guan, L. Qiu, Y. Zhang
and H. Peng, Recent advancement of nanostructured carbon for energy applications, Chem. Rev., 2015, 115, 5159-5223.

2. 1 L. Carrette, K. A. Friedrich and U. Stimming, Fuel cells – fundamentals and applications, Fuel cells., 2001, Vol.1, 5-39.

3. 1 S. K. Kamarudin, F. Achmad and W. R. W. Daud, Overview on the application of direct methanol fuel cell (DMFC) for portable electronic devices, Int. J. Hydrogen Energy., 2009, 34, 6902-6916.

4. 1 N. Kakati, J. Maiti, S. H. Lee, S. H. Jee, B. Viswanathan and Y. S. Yoon, Anode catalysts for direct methanol fuel cells in acidic media: do we have any alternative for Pt or Pt–Ru?, Chem. Rev., 2014, 114, 12397-12429.

5. 1 R. M. A. Hameed, R. S. Amin, K. M. El-Khatib and A. E. Fetohi, Preparation and characterization of Pt–CeO2/C and Pt–TiO2/C electrocatalysts with improved electrocatalytic activity for methanol oxidation, Appl. Surf. Sci., 2016, 367, 382-390.

6. 1 M. Khan, A.B. Yousaf, M. Chen, C. Wei, X. Wu, N. Huang, Z. Qi, L. Li, Mixed-phase Pd–Pt bimetallic alloy on graphene oxide with high activity for electrocatalytic applications, J. Power Sources., 2015, 282, 520-528.

7. 1 W. S. Hummers Jr and R. E. Offeman,Preparation of graphitic oxide, J. Am. Chem. Soc., 1958, 80, 1339-1339.

8. 1 Q. Sun, S.-J. Park and S. Kim, Preparation and electrocatalytic oxidation performance of Pt/MnO2–graphene oxide nanocomposites, Ind. Eng. Chem. Res., 2015, 26, 265-269.

9. 1 Y. Zhu, S. Murali, W. Cai, X. Li, J. W. Suk, J. R. Potts and R. S. Ruoff, Graphene and graphene oxide: synthesis, properties, and applications, Adv. Mater., 2010, 22, 3906-3924.

10 1 S. Themsirimongko, N. Promsawan and S. Saipanya, Noble Metal and Mn3O4 Supported Carbon Nanotubes: Enhanced Catalysts for Ethanol Electrooxidation, Int. J. Electrochem. Sci., 2016, 11, 967-982.

11. 1 A. Pinithchaisakula, S. Themsirimongkon, N. Promsawan, P. Weankeaw, K. Ounnunkad and S. Saipanya, An Investigation of a Polydopamine-Graphene Oxide Composite as a Support for an Anode Fuel Cell, Electro catalysis., 2016, 1-10.

12. 1Y. Zhao, L. Fan, H. Zhong, Y. Li and S. Yang, Platinum nanoparticle clusters immobilized on multiwalled carbon nanotubes: Electrodeposition and enhanced electrocatalytic activity for methanol oxidation, Adv. Funct. Mater., 2007, 17,

13.1 J. Chen, H. Peng, X. Wang, F. Shao, Z. Yuan and H. Han, Graphene oxide exhibits broad-spectrum antimicrobial activity against bacterial phytopathogens and fungal conidia by intertwining and membrane perturbation, Nanoscale., 2014, 6, 1879-1889.

14. 1T. Lammel, P. Boisseaux, M.-L. Fernández-Cruz and J. M. Navas, Internalization and cytotoxicity of graphene oxide and carboxyl graphene nanoplatelets in the human hepatocellular carcinoma cell line Hep G2, Part. Fibre Toxicol., 2013, 10, 27.

15.1 M. Andersson, L. Österlund, S. Ljungström and A. Palmqvist,Preparation of nanosize anatase and rutile TiO2 by hydrothermal treatment of microemulsions and their activity for
photocatalytic wet oxidation of phenol, J. Phys. Chem. B., 2002, 106, 10674-10679.

16. R. Vijayalakshmi and V. Rajendran, Synthesis and characterization of nano-TiO2 via different methods, Arch. App. Sci. Res., 2012, 4, 1183-1190.

17. H. Song, X. Qiu and F. Li, Effect of heat treatment on the performance of TiO2-Pt/CNT catalysts for methanol electrooxidation, Electrochim. Acta., 2008, 53, 3708-3713.

18. Y. Qu, Y. Gao, F. Kong, S. Zhang, L. Du and G. Yin, Pt–rGO–TiO2 nanocomposite by UV-photoreduction method as promising electrocatalyst for methanol oxidation, Int. J. Hydrogen Energy., 2013, 38, 12310-12317.

19. 1C. Patomnetikul, S. Thongtem and S. Narksitipan, Characterization of GO and TiO2-GO composites prepared by using microwave technique, Int. Soc. Opt. Photo., 2014, 923406-923406.

20. M. R. Gaeeni, M. Tohidian, M. Sasani Ghamsari and M. H. Majles Ara,Synthesis of graphene oxide-TiO2 nanocomposite as an adsorbent for the enrichment and determination of rutin, J. Nanomed., 2015, 2, 269-272.

21. Y. Yuying, Z. Zhang and H. Zhongai, Activity improvement of Pt/C catalysts by adding CeO2 nanoparticles, J. Rare Earths., 2011, 29, 58-63.

22. 1 Y. Li, W. Gao, L. Ci, C. Wang, P.M. Ajayan, Catalytic performance of Pt nanoparticles on reduced graphene oxide for methanol electro-oxidation, Carbon., 2010, 48, 1124-1130.

23. Z.-x. Cai, C.-c. Liu, G.-h. Wu, X.-m. Chen, X. Chen, Green synthesis of Pt-on-Pd bimetallic nanodendrites on graphene via in situ reduction, and their enhanced electrocatalytic activity for methanol oxidation, Electrochimica Acta., 2014, 127, 377-383.

24. Y. Liu, M. Chi, V. Mazumder, K.L. More, S. Soled, J.D. Henao, S. Sun, Composition-controlled synthesis of bimetallic PdPt nanoparticles and their electro-oxidation of methanol, Chemistry of Materials., 2011, 23, 4199-4203.

25. 1 R. M. Hameed, R. S. Amin, K. M. El Khatib and A. E. Fetohi, Influence of Metal Oxides on Platinum Activity towards Methanol Oxidation in H2SO4 solution, Chem. Phys. Chem., 2016, 17, 1054-1061.