Anomalous Electrochemical Dissolution and Passivation of Iron Growth Catalysts in Carbon Nanotubes

Abstract

Catalytically synthesized carbon nanotubes (CNTs) such as those prepared via chemical vapor deposition (CVD) contain metallic impurities including Fe, Ni, Co, and Mo. Transition metal contaminants such as Fe can participate in redox cycling reactions that catalyze the generation of reactive oxygen species and other products. Through the nature of the CVD growth process, metallic nanoparticles become encased within the CNT graphene lattice and may still be chemically accessible and participate in redox chemistry, especially when these materials are utilized as electrodes in electrochemical applications. We demonstrate that metallic impurities can be selectively dissolved and/or passivated during electrochemical potential cycling. Anomalous Fe dissolution and passivation behavior is observed in neutral (pH=6.40+/-0.03) aqueous solutions when using multiwalled CNTs prepared from CVD. Fe particles contained within these CNTs display intriguing, potential-dependent Fe redox activity that varies with supporting electrolyte composition. In neutral solutions containing dibasic sodium phosphate, sodium acetate, and sodium citrate, FeII dissolution and surface confined FeII/III redox activity are significant despite Fe being encapsulated within CNT graphene layers. However, no apparent Fe dissolution is observed in 1 M potassium nitrate solutions, suggesting that the electrolyte composition plays an important role in observing FeII dissolution, passivation, and surface confined FeII/III redox activity. Between potentials of 0 and -1.1 V versus Hg/Hg2SO4, the primary redox-active Fe species are surface FeII/III oxides/oxyhydroxides. This FeII/III surface oxide redox chemistry can be completely suppressed by passivating Fe through repeated cycling of the CNTs in supporting electrolyte. By increasing the potential to more negative values (>-1.3 V), FeII dissolution may be induced in electrolyte solutions containing acetate and phosphate and inhibited by addition of sodium benzoate, which adsorbs on exposed Fe particles, effectively passivating them. Finally, we observe that the FeII/III redox chemistry or subsequent passivation does not affect the onset of oxygen reduction at nitrogen-doped CNTs, suggesting that the surface-bound FeII species is not the primary catalytically active site for oxygen reduction in these materials.