Skip to main content Accessibility help

Investigation of ORR Performances on Graphene/Phthalocyanine Nanocomposite in Neutral Medium

  • Moumita Mukherjee (a1), Madhupriya Samanta (a2) (a3), Gour P. Das (a1) and Kalyan K. Chattopadhyay (a3)


The drive to replace scarce and expensive Pt-based electrocatalysts for oxygen reduction reaction (ORR) has led to the development of a group of electrocatalysts composed of transition-metal ion centers coordinated with four nitrogen groups (M-N4). Among these, metal phthalocyanines (MPcs), due to low cost of preparation, highly conjugated structure as well as high thermal and chemical stability, have received a great interest. The catalytic activity of MPcs can be improved by employing conducting supports. Here, in this report, we have solvothermally synthesized graphene-supported zinc phthalocyanine nanostructures, and their ORR kinetics and mechanism have been investigated in neutral solution (pH = 7) by using the rotating disk electrode technique. The as-synthesized nanocomposite followed a 4e reduction pathway. The onset potential (−0.04 V versus Ag/AgCl) found in this work can be comparable with other state-of-the-art material, demonstrating good performance in neutral solution. The fascinating performance leads the nanocomposite material toward future energy applications.


Corresponding author

*Authors for correspondence: Gour P. Das, E-mail:; Kalyan K. Chattopadhyay, E-mail:


Hide All

Present address: Department of Metallurgical and Materials Engineering, Indian Institute of Technology, Kharagpur 721 302, West Bengal, India.



Hide All
Ahmed, J, Yuan, Y, Zhoud, L & Kima, S (2012). Carbon supported cobalt oxide nanoparticles–iron phthalocyanine as alternative cathode catalyst for oxygen reduction in microbial fuel cells. J Power Sources 208, 170175.
Cao, C, Wei, L, Su, M, Gang Wang, G & Shen, J (2016). Spontaneous bubble-template assisted metal–polymeric framework derived N/Co dual-doped hierarchically porous carbon/Fe3O4 nanohybrids: Superior electrocatalyst for ORR in biofuel cells. J Mater Chem A 4, 93039310.
Choi, HJ, Ashok Kumar, N & Baek, JB (2015). Graphene supported non-precious metalmacrocycle catalysts for oxygen reduction reaction in fuel cells. Nanoscale 7, 69916998.
Chu, Y, Gu, L, Ju, X, Du, H, Zhao, J & Qu, K (2018). Carbon supported multi-branch nitrogen-containing polymers as oxygen reduction catalysts. Catalysts 8, 245266.
Cui, L, Lv, G, Dou, Z & He, X (2013). Fabrication of iron phthalocyanine/graphene micro/nanocomposite by solvothermally assisted π–π assembling method and its application for oxygen reduction reaction. Electrochim Acta 106, 272278.
Ejaz, A & Jeon, S (2018). The individual role of pyrrolic, pyridinic and graphitic nitrogen in the growth kinetics of Pd NPs on N-rGO followed by a comprehensive study on ORR. Int J Hydrogen Energy 43, 56905702.
Geim, AK & Novoselov, KS (2007). The rise of graphene. Nat Mater 6, 183191.
Hummers, WS Jr. & Offeman, RE (1958) Preparation of graphitic oxide. J Am ChemSoc 80, 1339.
Jasinski, R (1964). A new fuel cell cathode catalyst. Nature 201, 12121213.
Jiang, Y, Lu, Y, Lv, X, Han, D, Zhang, Q, Niu, L & Chen, W (2013). Enhanced catalytic performance of Pt-free iron phthalocyanine by graphene support for efficient oxygen reduction reaction. ACS Catal 3, 12631271.
Koca, A, Kalkan, A & Bayır, ZA (2011). Electrocatalytic oxygen reduction and hydrogen evolution reactions on phthalocyanine modified electrodes: Electrochemical, in situ spectroelectrochemical, and in situ electrocolorimetric monitoring. Electrochim Acta 56, 55135525.
Li, X, Cai, W, An, J, Kim, S, Nah, J, Yang, D, Piner, R, Velamakanni, A, Jung, I, Tutuc, E, Banerjee, SK, Colombo, L & Ruoff, RS (2009). Large-area synthesis of high-quality and uniform graphene films on copper foils. Science 324, 13121314.
Mukherjee, M, Samanta, M, Ghorai, UK, Murmu, S, Das, GP & Chattopadhyay, KK (2018). One pot solvothermal synthesis of ZnPc nanotube and its composite with RGO: A high performance ORR catalyst in alkaline medium. Appl Suf Sci 449, 144151.
Nagaiah, TC, Maljusch, A, Chen, X, Bron, M & Schuhmann, W (2009). Visualization of the local catalytic activity of electrodeposited Pt–Ag catalysts for oxygen reduction by means of SECM. Chem Phys Chem 10, 27112718.
Reina, A, Jia, X, Ho, J, Nezich, D, Son, H, Bulovic, V, Dresselhaus, MS & Kong, J (2009). Large area, Few-layer graphene films on arbitrary substrates by chemical vapor deposition. Nano let 9, 3035.
Roy, D, Das, NM, Shakti, N & Gupta, PS (2014). Comparative study of optical, structural and electrical properties of zinc phthalocyanine Langmuir–Blodgett thin film on annealing. RSC Adv 4, 4251442522.
Sakamoto, K & Ohno-Okumura, E (2009). Synthesis and functional properties of phthalocyanines. Materials (Basel) 2, 11271180.
Sedona, F, Marino, MD, Forrer, D, Vittadini, A, Casarin, M, Cossaro, A, Floreano, L, Verdini, A & Sambi, M (2012). Tuning the catalytic activity of Ag(110)-supported Fe phthalocyanine in the oxygen reduction reaction. Nat Mater 11, 970977.
Shinagawa, T & Takanabe, K (2016). Electrolyte engineering toward efficient hydrogen production electrocatalysis with oxygen-crossover regulation under densely buffered near-neutral pH conditions. J Phys Chem C 120, 17851794.
Tong, X, Xia, X, Guo, C, Zhang, Y, Tu, J, Fan, HJ & Guo, X-Y (2015). Efficient oxygen reduction reaction using mesoporous Ni-doped Co3O4nanowire array electrocatalysts. J Mater Chem A 3, 1837218379.
Vincent, I & Bessarabov, D (2016). Electrochemical characterization and oxygen reduction kinetics of Cu-incorporated cobalt oxide catalyst. Int J Electrochem Sci 11, 80028015.
Wen, Z, Ci, S, Zhang, F, Feng, X, Cui, S, Mao, S, Luo, S, He, Z & Chen, J (2012). Nitrogen-enriched core-shell structured Fe/Fe3C-C nanorods as advanced electrocatalysts for oxygen reduction reaction. Adv Mater 24, 13991404.
Xu, X, Wang, M, Liu, Y, Lu, T & Pan, L (2016). Metal–organic framework-engaged formation of a hierarchical hybrid with carbon nanotube inserted porous carbon polyhedra for highly efficient capacitive deionization. J Mater Chem A 4, 54675473.
Yang, L, Jiang, S, Zhao, Y, Zhu, L, Chen, S, Wang, X, Wu, Q, Ma, J, Ma, Y & Hu, Z (2011). Boron-doped carbon nanotubes as metal-free electrocatalysts for the oxygen reduction reaction. Angew Chem Int Ed Engl 50, 71327135.
Zhang, W, Shaikh, AU, Tsui, EY & Swager, TM (2009). Cobalt porphyrin functionalized carbon nanotubes for oxygen reduction. Chem Mater 21, 32343241.
Zhang, C, Hao, R, Yin, H, Liu, F & Hou, Y (2012). Iron phthalocyanine and nitrogen-doped graphene composite as a novel non-precious catalyst for the oxygen reduction reaction. Nanoscale 4, 73267329.
Zhang, S, Zhang, H, Hua, X & Chen, S (2015). Tailoring molecular architectures of Fe phthalocyanine on nanocarbon supports for high oxygen reduction performance. J Mater Chem A 3, 1001310019.
Zhu, S, Hu, X, Zhang, L & Shao, M (2016). Impacts of perchloric acid, nafion, and alkali metal ions on oxygen reduction reaction kinetics in acidic and alkaline solutions. J Phys Chem C 120, 2745227461.


Investigation of ORR Performances on Graphene/Phthalocyanine Nanocomposite in Neutral Medium

  • Moumita Mukherjee (a1), Madhupriya Samanta (a2) (a3), Gour P. Das (a1) and Kalyan K. Chattopadhyay (a3)


Full text views

Total number of HTML views: 0
Total number of PDF views: 0 *
Loading metrics...

Abstract views

Total abstract views: 0 *
Loading metrics...

* Views captured on Cambridge Core between <date>. This data will be updated every 24 hours.

Usage data cannot currently be displayed