The discovery that cobalt phthalocyanine catalyzed the oxygen reduction reaction (ORR) by Jasinski launched the development and study of many non-precious metal and nitrogen-containing ORR electrocatalysts such as metalloporphyrins.1,2 However, despite years of study, very little is known about the active site and mechanism of oxygen reduction in these materials. Recently, several small molecule probes of the ORR active site for Fe-N-C electrocatalysts have been proposed, including CO, CN-, and N3-.3-5 However, there is still no clear picture of how O2 is bound to and reduced by these catalysts.Graphene, a two-dimensional material consisting of sp2 hybridized carbon, has received relatively large amounts of attention due to its high electrical conductivity, large surface area, and good thermal and chemical stability. Recently, graphene enhanced Raman spectroscopy (GERS) has been used to study adsorbed small molecules.6 By supporting an ORR electrocatalyst, such as a metalloporphyrin or metallophthalocyanine, on a graphene support grown via chemical vapor deposition, we analyze changes during oxygen binding and reduction to potentially unravel the ORR mechanism in the Fe-N-C materials.(1) Jasinski, R. J. J. Electrochem. Soc. 1965  , 112, 526(2) Jasinski, R. J. Nature 1964  , 201, 1212.(3) Oberst, J. L.; Thorum, M. S.; Gewirth, A. A. J. Phys. Chem. C 2012  , 116, 25257.(4) Thorum, M. S.; Hankett, J. M.; Gewirth, A. A. J. Phys. Chem. Lett. 2011  , 2, 295.(5) Birry, L.; Zagal, J. H.; Dodelet, J.-P. Electrochem. Commun. 2010  , 12, 628.(6) Ling, X.; Xie, L.; Fang, Y.; Xu, H.; Zhang, H.; Kong, J.; Dresselhaus, M. S.; Zhang, J.; Liu, Z. Nano Letters 2010  , 10, 553.

Graphene-enhanced Raman spectroscopy to study oxygen reduction in non-precious metal electrocatalysts

246th National Meeting (2013)

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