Phosphate tolerance of nitrogen-coordinated-iron-carbon (FeNC) catalysts for oxygen reduction reaction: A size-related hindrance effect.

• FeNC is a promising cathode catalyst for phosphoric acid fuel cells. • ORR activity of FeNC is projected to be comparable to Pt/C at higher temperatures. • Unlike Pt/C, FeNC is unexpectedly resistant to poisoning by phosphate anions. • A "size-related hindrance effect" is observed during phosphate exposure on FeNC. • Phosphate poisoning of FeNC depends strongly on the nature of carbon support. The greatest challenges facing the large – scale commercialization of the intermediate temperature phosphoric acid fuel cell (PAFC) technology are: (i) the high cost of Pt catalyst that is required to overcome the slow kinetics of oxygen reduction reaction (ORR) on the PAFC cathode, and (ii) deactivation of the Pt catalyst by exposure to the phosphoric acid electrolyte. Inexpensive carbon-based materials, particularly iron-nitrogen-coordinated carbon supported catalysts (FeNC), are promising cathodes for PAFCs. The higher ORR activation energy and phosphate poisoning resistance of FeNC present a clear advantage over the Pt-based commercial catalysts that are easily susceptible to deactivation after exposure to phosphate anions. While the immunity of FeNC catalysts to phosphate anion poisoning has been reported previously, this work explores the counter-intuitive and conditional nature of this poisoning resistance based on the properties of the carbon support used in the preparation of the FeNC catalyst. A combination of electrochemical measurements with characterization experiments performed using X-ray photoelectron spectroscopy, infrared spectroscopy and in-situ X-ray absorption spectroscopy is used to explore the phenomenon of phosphate poisoning on FeNC catalysts synthesized from two different carbon supports. Results from these studies reveal a "size-related hindrance effect" wherein the ORR active Fe centers in FeNC remain inaccessible to larger anions such as phosphate when the Fe sites are present deeper inside the pores of a carbon support with high porosity. However, FeNC catalyst is poisoned by phosphate anions when synthesized using a carbon support with low porosity. This work helps gain insights into the nature of active sites in FeNC catalysts that will be useful in designing precious-metal free ORR catalysts for intermediate temperature fuel cell technologies. [ABSTRACT FROM AUTHOR]