Aligned silver nanoparticles anchored on pyrrolic and pyridinic-nitrogen induced carbon nanotubes for enhanced oxygen reduction reaction

Abstract

Comprehension of the metal-nanostructure arrays is of great significance for the rational design of the cathode catalyst for the oxygen reduction reaction (ORR). Therefore, we fabricated a cathode catalyst consisting of the small-size, aligned silver nanoparticles (Ag NPs) embedded into the pyrrolic and pyridinic-Nitrogen functionalized carbon nanotubes. The N-defected structure was prepared by acidification of carbon nanotubes (CNTs) to avoid inherited stacking of its layers followed by the introduction of 2,7 diaminophenazine (DPA) using a hydrothermal process, while small-size Ag NPs were aligned through electrodeposition onto the N-defected carbon nanotube (CNT-DPA-Ag). The individual role of pyrrolic and pyridinic -N in the electrocatalytic ORR performance, synthesis of small size, and distribution behavior of Ag NPs were evaluated. To maximize the ORR performance of the catalyst, the advantage was taken from the presence of carbon atoms next to the pyridinic-N which is a Lewis base and acts as an adsorption and protonation site for the oxygen (O2) molecule and eventually ensures a direct 4e− transfer route for the electrochemical conversion of O2 into water (H2O). Transmission electron microscopy (TEM) analysis of CNT-DPA-Ag revealed a small size, aligned Ag NPs (average size 2 nm) resulting in a large surface area and rich electroactive sites for adsorption of O2. The CNT-DPA-Ag showed a remarkable ORR performance in terms of positive onset potential (-0.052 V), high diffusion-limiting current density (-5.54 mAcm−2), and noteworthy methanol tolerance, and long-term durability in comparison to the commercial 20 wt% Pt/C.