Myoglobin-based non-precious metal carbon catalysts for an oxygen reduction reaction

A non-precious metal catalyst (NPMC) promoting a four-electron oxygen reduction reaction (ORR) was synthesized by heat treatment of myoglobin (Mb) containing a heme (iron protoporphyrin IX) as a source of iron, nitrogen, and carbon atoms. Samples of the mixture of Mb and carbon black (Vulcan XC72R: VC) were pyrolyzed at 740, 840, 940, 1040 or 1140°C under N₂ flow. The microstructures of the carbonized Mb catalysts were characterized by XRD, Raman spectroscopy, XPS, and TEM. Results indicate that the iron-containing active site is embedded within the surface structure in an amorphous domain of the carbon materials. The catalyst ink in a 0.05 wt% Nafion solution in isopropanol was coated onto a glassy carbon electrode and the ORR activity of Mb-based NPMCs was evaluated in a rotating disk electrode experiment in an O₂-saturated 0.1 M HClO₄ solution at 25°C. The catalyst synthesized at 940°C has the highest ORR activity in terms of the onset potential and the current density. In contrast, pyrolytic temperatures above 940°C decrease the activity, suggesting that the active structure of the catalyst apparently decomposes at higher temperatures. The Koutecky-Levich plots indicate that the Mb-based catalyst prepared at 940°C catalyzes four-electron ORR (n = ca. 4). The catalysts prepared at other temperatures have n values of 3.6 at 740°C, 3.7 at 840°C, and 2.9 at 1040°C. The ORR of Mb/VC is diffusion-controlled at potentials lower than 0.3 V (vs. RHE) and the onset potential is 0.84 ± 0.01 V.