Influence of Iron Salt Anions on Formation and Oxygen Reduction Activity of Fe/N-Doped Mesoporous Carbon Fuel Cell Catalysts.

Doping carbon materials with transition metal ions can greatly expand their utility, given these metal ions' unique catalytic activity, for example, in oxygen reduction in proton exchange membrane fuel cells. Unlike main group dopants, a counter anion to the metal cation must be selected and this choice has hitherto received little attention for this synthesis method. Herein, we describe the profound effects that the anion has on the resultant iron/nitrogen-doped ordered mesoporous carbons (Fe-OMC). To increase the iron loading and the number of iron-centered catalytically active sites, we selected three iron salts Fe(OAc), Fe(OTf), and Fe(BF)·6HO, which show greatly enhanced solubility in the liquid carbon precursor (furfurylamine) compared to FeCl·6HO. The increased solubility leads to a significantly higher iron loading in the Fe-OMC prepared with Fe(OTf), but the increase in performance as cathode catalysts in fuel cells is only marginal. The Fe-OMCs prepared with Fe(OAc) and Fe(BF)·6HO exhibited similar or lower iron loadings compared to the Fe-OMC prepared with FeCl·6HO despite their much higher solubilities. Most importantly, the different iron salts affect not only the final iron loading, but also which type of iron species forms in the Fe-OMC with different types showing different catalytic activity.